Ink jet faceplate coatings comprising structured organic films

ABSTRACT

A coating for an ink jet printhead front face, wherein the coating comprises a structured organic film (SOF) comprising a plurality of segments, a plurality of linkers arranged as a covalent organic framework. Methods for preparing a coating for an ink jet printhead front face, wherein the coating comprises a SOF are also disclosed.

CROSS-REFERENCE TO RELATED APPLICATIONS

This nonprovisional application is related to U.S. patent applicationSer. No. 12/716,524, now U.S. Pat. No. 8,093,347; Ser. Nos. 12/716,449;12/716,706; 12/716,324; 12/716,686; 12/716,571; 12/815,688; 12/845,053;12/845,235; 12/854,962, now U.S. Pat. No. 8,119,315; Ser. No.12/854,957, now U.S. Pat. No. 8,119,314; and Ser. No. 12/845,052entitled “Structured Organic Films,” “Structured Organic Films Having anAdded Functionality,” “Mixed Solvent Process for Preparing StructuredOrganic Films,” “Composite Structured Organic Films,” “Process ForPreparing Structured Organic Films (SOFs) Via a Pre-SOF,” “ElectronicDevices Comprising Structured Organic Films,” “Periodic StructuredOrganic Films,” “Capped Structured Organic Film Compositions,” “ImagingMembers Comprising Capped Structured Organic Film Compositions,”“Imaging Members for Ink-Based Digital Printing Comprising StructuredOrganic Films,” “Imaging Devices Comprising Structured Organic Films,”and “Imaging Members Comprising Structured Organic Films,” respectively;and U.S. Provisional Application No. 61/157,411, entitled “StructuredOrganic Films” filed Mar. 4, 2009, the disclosures of which are totallyincorporated herein by reference in their entireties.

BACKGROUND OF THE INVENTION

The present disclosure is generally directed, in various embodiments, tocoatings for print heads. More particularly, the disclosure relates to acoating for a front face of an ink jet printhead, such as ananti-fouling coating for ink jet faceplates. Additionally, disclosedherein is a coating that prevents wetting, drooling, and flooding ofink, such as ultra-violet curable ink and solid ink on an ink jetprinthead front face.

Fluid ink jet systems generally include one or more printheads having aplurality of ink jets from which drops of fluid are ejected towards arecording medium. The ink jets of a printhead typically receive ink froman ink supply chamber or manifold in the printhead that, in turn,receives ink from a source, such as a melted ink reservoir or an inkcartridge. Each ink jet may include a channel having one end in fluidcommunication with the ink supply manifold. The other end of the inkchannel generally has an orifice or nozzle for ejecting drops of ink.The nozzles of the ink jets may be formed in an aperture or nozzle platethat has openings corresponding to the nozzles of the ink jets. Duringoperation, drop ejecting signals activate actuators in the ink jets toexpel drops of fluid from the ink jet nozzles onto the recording medium.By selectively activating the actuators of the ink jets to eject dropsas the recording medium and/or printhead assembly are moved relative toone another, the deposited drops can be precisely patterned to formparticular text and graphic images on the recording medium. An exampleof a full width array printhead is described in U.S. Patent PublicationNo. 2009/0046125, which is hereby incorporated by reference herein inits entirety. An example of an ultra-violet curable ink that can bejetted in such a printhead is described in U.S. Patent Publication No.2007/0123606, which is hereby incorporated by reference herein in itsentirety. An example of a solid ink which can be jetted in such aprinthead is the Xerox ColorQube™ cyan solid ink available from XeroxCorporation.

One difficulty faced by fluid ink jet systems is wetting, drooling orflooding of inks onto the printhead front face. This may occur as aresult of ink contamination of the printhead front face. FIG. 1 is aphotograph of a printhead front face after a printing run showingwetting and contamination of an ink over a large area of the front face.The contaminated front face can cause or contribute to non-firing ormissing drops, undersized or otherwise wrong-sized drops, satellites, ormisdirected drops on the recording medium and thus result in degradedprint quality.

Several material-based approaches are being explored to address thisproblem, such as, for example, adding hydrophobic properties to a filmfor use as a layer on the printhead front face. Introducinghydrophobicity usually involves integrating fluorine content into thematerial. However, this is generally not a straightforward procedure:blending Teflon, Viton, or custom fluorinated polymers can bechallenging due to their poor solubility with the nominal components ofa given film. Integrating fluorinated small molecules is generally amore facile option; however achieving a stable dispersion and thepropensity for phase separation and leaching from the film are commonroad blocks toward implementation. Conventional approaches also includethe use of low surface energy fluoropolymer-based coatings. Thesecoatings have poor adhesion to the inkjet faceplate materials (stainlesssteel and polyimide) resulting in short lifetimes for the inkjet printheads. The poor adhesion of the current fluorpolymers to the stainlesssteel faceplate results in flaking and pealing of the coating duringprint head handling and cleaning. Thus, compositions, such as the SOFsof the present disclosure, where fluorine can be readily integrated(chemically bonded) and evenly dispersed within their structures offervast improvements over conventional films, especially since the fluorinecontent can be logically, systematically, and easily adjusted.

Maintenance procedures have been implemented in ink jet printers forpreventing and clearing ink jet blockages and for cleaning the printhead front face. A maintenance procedure for ink jet printers isdescribed in U.S. Patent Publication No. 2008/0316247, which is herebyincorporated by reference in its entirety. Examples of maintenanceprocedures include jetting or purging ink from the ink jet channels andnozzles and wiping the printhead front face. Jetting procedurestypically involve ejecting a plurality of drops from each ink jet inorder to clear contaminants from the jets. Purging procedures typicallyinvolve applying an air pressure pulse to the ink reservoir to cause inkflow from all of the jets. The jetted ink may be collected in a wastereservoir such as a spittoon. The purged ink may be collected in a wastereservoir such as a waster tray. A wetted, contaminated printhead frontface interferes with the collecting of the purged ink by preventing orreducing the ability of the ink to slide over the front face into thewaste reservoir. Wiping procedures are usually performed by a wiperblade that moves relative to the nozzle plate to remove ink residue, aswell as any paper, dust, or other debris that has collected on the printhead front face. An example of a wiper assembly is described in U.S.Pat. No. 5,432,539, which is hereby incorporated by reference herein inits entirety. Jetting/purging and wiping procedures may each beperformed alone or in conjunction with one another. For example, awiping procedure may be performed after ink is purged through the jetsin order to wipe excess ink from the nozzle plate.

In view of such handling and cleaning procedures, there is a need for aninkjet faceplate material that has good adhesion to the faceplate, isthermally stable, is mechanically and chemically robust (particularlyimportant for UV curable or other chemically reactive or agressiveinks). A further need exists for an improved printhead front facecoating that reduces or eliminates wetting, drooling, or flooding ofink, such as UV or solid ink, over the printhead front face. There alsoremains a need for an improved printhead front face coating that isrobust (i.e., does not flaking and pealing of the coating during printhead handling and cleaning) to withstand the various maintenanceprocedures applied to the printhead front face.

SUMMARY OF THE DISCLOSURE

There is provided in embodiments a coating for an ink jet printheadfront face, wherein the coating comprises a structured organic film(SOF) comprising a plurality of segments, a plurality of linkersarranged as a covalent organic framework (COF). In embodiments, whensuch a coating is disposed on an ink jet printhead front face surface,jetted drops of ink, such as ultra-violet curable ink or solid ink,exhibit very little adhesion towards the surface. In embodiments, thecoating provides this property even after many cleaning cycles (such asmore than 200 cleaning or wiping cycles, or more than 500 cleaning orwiping cycles) thereby preventing ink contamination and allowing inkdroplets to roll off the front face leaving behind no residue.

In further embodiments, a printing apparatus comprising an ink jetprinthead comprises a front face having disposed on a surface thereof acoating comprising a structured organic film (SOF) comprising aplurality of segments, a plurality of linkers arranged as a covalentorganic framework (COF) wherein jetted drops of ink, such asultra-violet curable ink or solid ink, exhibit a contact angle of fromabout 140° to about 60°, such as a contact angle of about 110° to about75°. When ink is filled into the printhead, it is desired to maintainthe ink within the nozzle until it is time to eject the ink. Generally,the greater the ink contact angle the better (higher) the holdingpressure. Holding pressure measures the ability of the aperture plate toavoid ink weeping out of the nozzle opening when the pressure of the inktank (reservoir) increases. Advantageously, the present coatingsproviding in combination low adhesion and high contact angle forultra-violet curable ink and solid ink which further provides thebenefit of improved holding pressure or reduced or eliminated weeping ofink out of the nozzle.

BRIEF DESCRIPTION OF THE DRAWINGS

Other aspects of the present disclosure will become apparent as thefollowing description proceeds and upon reference to the followingfigures which represent illustrative embodiments:

FIG. 1 is a photograph exemplifying how inks weep and drool fromconventional inkjet print heads after a printing run.

FIG. 2 is an illustration of a cross-section of a printhead front facehaving a coating disposed thereon in accordance with the presentdisclosure.

FIG. 3 an illustration of a cross-section of another printhead frontface having a coating disposed thereon in accordance with the presentdisclosure.

FIGS. 4A-O are illustrations of exemplary building blocks whosesymmetrical elements are outlined.

DETAILED DESCRIPTION

The coatings of the present disclosure resist contamination, droolingand flooding by inks, such as ultra-violet (UV) curable and UV curablephase change inks and solid inks (also referred to as phase changeinks), and maintain this resistance even after numerouspurge/maintenance cycles. The present disclosure demonstrates that SOFshave good adhesion to polyimide and stainless steel (ink jet faceplatematerials), have high thermal stability, and allow solid inks and UVcurable inks to easily wick from the surface even after prolongedexposure times.

The coatings comprising structured Organic Films (SOFs) of the presentdisclosure may be applied to a variety of substrates, includingstainless steel and polyimide, using a variety of solution-basedprocessing methods (spray, dip, blade coatings) yielding a suitablethickness predetermined by the user. The coatings comprising a SOF maybe selected to have strong adhesion to stainless steel and polyimidewithout the need for surface modification or the use of promoters. Thecoatings comprising SOFs of the present disclosure are thermally stable(>200 C for prolonged periods of time, no observable change or damageafter 45 days, and may be tailored to have anti-wetting and non-stickinteractions with inks, such as solid ink or UV curable ink, whichallows the inks to easily wick from the surface even after prolongedexposure times. The coatings comprising a SOF are resistant to surfacewear or damage.

Additionally, the tunability of structured organic film compositionsmakes them an attractive materials platform for anti-fouling coatings ingeneral, one example being anti-fouling coatings for inkjet face plates.

Exemplary embodiments disclosed herein provide materials and methods forink jet printhead nozzle plate and related printing apparatus. Inembodiments, the coating comprising a SOF may be formed on a substrate,for example, a printhead nozzle plate substrate for ink jet printheadapplications. In embodiments, the SOF in the coating may have an addedfunctionality such as an oleophobic or hydrophobic added functionality.

In embodiments, the present coatings exhibit very low adhesion withinks, such as UV ink and solid ink, as measured by a ink wicking test sothat ink drops on the printhead front face are removed and leave noresidue. The ink jet printhead front face coatings herein enableproduction of high quality, high throughput, digitally printed imageswith inks, such as ultra-violet curable ink or solid ink, that areejected from a printhead, wherein the images are free of print defectsdue to misdirected droplets or missing jets caused by front facedrooling of the ink experienced with previous printhead front facecoatings.

In embodiments, jetted drops of ultra-violet curable ink or jetted dropsof solid ink can exhibit a contact angle with the coating layercomprising a SOF of from about 140° to about 60°, or from about 110° toabout 75°, or from about 100° to about 85°. When ink is filled into theprinthead, it is desired to maintain the ink within the printhead nozzleuntil it is time to eject the ink. Generally, the greater the inkcontact angle, the better (or higher) the holding (or drooling)pressure. The great contact angle of the above coating layer comprisinga SOF of the printhead nozzle plate can improve de-wetting and jettedink drop quality as well as eliminate weeping. As disclosed herein, theterm “holding pressure” measures the ability of an aperture nozzle plateto avoid ink weeping out of the nozzle opening when the pressure of theink tank (reservoir) increases. Advantageously, the disclosed coatinglayer comprising a SOF provided in combination with low adhesion andhigh contact angle with UV curable ink and solid ink can further providean improved holding pressure and/or reduced/eliminated weeping of inkout of the nozzle.

In this specification and the claims that follow, singular forms such as“a,” “an,” and “the” include plural forms unless the content clearlydictates otherwise.

The term “SOF” generally refers to a covalent organic framework (COF)that is a film at a macroscopic level. The phrase “macroscopic level”refers, for example, to the naked eye view of the present SOFs. AlthoughCOFs are a network at the “microscopic level” or “molecular level”(requiring use of powerful magnifying equipment or as assessed usingscattering methods), the present SOF is fundamentally different at the“macroscopic level” because the film is for instance orders of magnitudelarger in coverage than a microscopic level COF network. SOFs describedherein that may be used in the embodiments described herein are solventresistant and have macroscopic morphologies much different than typicalCOFs previously synthesized.

The coatings disclosed herein exhibit suitable abrasion characteristicsfor use as surface coatings for the printhead to avoid excessive wearupon usage or wiping. In embodiments, the coatings of the presentdisclosure include a structured organic film (SOF) comprising aplurality of segments, a plurality of linkers arranged as a covalentorganic framework (COF) and optionally, in specific embodiments, a SOFcomprising a fluorinated segment. Exemplary fluorinated SOFs aredescribed in U.S. patent application Ser. No. 13/173,948, now U.S. Pat.No. 8,247,142, to Adrien P. Cote and Matthew A. Heuft entitled“Fluorinated Structured Organic Film Compositions,” which is being filedconcurrently with the present application, the disclosure of which istotally incorporated herein by reference in its entirety.

Designing and tuning the fluorine content in the SOF compositions of thepresent disclosure is straightforward and does not require synthesis ofcustom polymers nor require blending/dispersion procedures. Furthermore,the SOF compositions of the present disclosure may be SOF compositionsin which the fluorine content is uniformly dispersed and patterned atthe molecular level.

The coatings may be disposed on a printhead, such as on a printheadfront face. Any suitable method can be used for applying the coating(s)to the surface of the printhead. Suitable techniques for applying thecoating include solution based, spray, dip, blade coatings and thosediscussed below.

The printhead aperture plate (or orifice plate or print head front faceplate) may be made of any suitable material and may be of anyconfiguration suitable to the device. Orifice plates of square orrectangular shapes are typically selected due to ease of manufacture.Orifice plates may be made of any suitable composition. In embodiments,aperture plates or orifice plates are composed of stainless steel,steel, nickel, copper, aluminum, polyimide, silicon or SOFs. Orificesplates can also be made of stainless steel selectively plated with abraze material such as gold.

The coatings of the present disclosure may be used with any type ofprint head. Referring to FIG. 2, a printhead 200 having the coating ofthe present disclosure, which comprises an SOF, disposed thereon isillustrated. Printhead 200 includes a base substrate 202 withtransducers 204 on one surface and acoustic lenses 206 on an oppositesurface. Spaced from the base substrate 202 is a liquid level controlplate 208. A coating 210 in accordance with the present disclosure isdisposed along plate 208. In embodiments, the coating comprising a SOFmay have a thickness ranging from about 10 nm to about 100 μm, such asranging from about 50 nm to about 20 μm, or ranging from about 100 nm toabout 10 μm.

The base substrate 202 and the liquid level control plate 208 define achannel, which holds a flowing liquid 212. The liquid level controlplate 208 contains an array 214 of apertures 216. The transducers 204,acoustic lenses 206, and apertures 216 are all axially aligned such thatan acoustic wave produced by a single transducer 204 will be focused byits aligned acoustics 206 at approximately a free surface 218 of theliquid 212 in its aligned aperture 216. When sufficient power isobtained a droplet is emitted from surface 218.

FIG. 3 illustrates another embodiment of a printhead 300 having acoating disposed thereon in accordance with the present disclosure. InFIG. 3, a drop on demand ink jet print head 300 has a body 302 thatincludes one or more ink pressures chambers 304 coupled to or incommunication with one or more ink sources 306. Ink jet print head 300has one or more ink ejection means such as orifices or nozzle/outlets308. A typical ink jet printer includes a plurality of ink pressurechambers 304 with each pressure chamber 304 coupled to one or morenozzle/outlets 308. For simplification, a single outlet 308 isillustrated in FIG. 3. Each nozzle/outlet 308 is coupled to or incommunication with an ink pressure chamber 304 by way of an ink passageindicated by arrows 310. Ink passes through nozzle/outlet 308 during inkdrop formation. Ink drops travel in a direction along path 310 fromnozzle outlets 308 toward a print medium (not shown) that is spaced fromnozzle/outlets 308. Nozzle/outlets 308 can be formed in an orifice plateor print head front face plate 312 contained on body 302 on the outletside of the ink jet print head 300. A coating 314 in accordance with thepresent disclosure is disposed along the orifice plate 312.

In embodiments, the printhead comprises a front face having disposed ona surface thereof a low adhesion coating comprising a structured organicfilm (SOF) comprising a plurality of segments, a plurality of linkersarranged as a covalent organic framework (COF), wherein jetted drops ofink, such as ultra-violet curable ink or solid ink, exhibit a contactangle of from about 140° to about 60° in specific embodiments a contactangle greater than about 110° or greater than about 75° with the surfacecoating. Generally, the greater the ink contact angle the higher theholding pressure. As discussed above, holding pressure measures theability of the aperture plate to avoid ink weeping out of the nozzlewhen the pressure of the ink tank (reservoir) increases. In embodiments,the coatings of the present disclosure provide in combination lowadhesion and high contact angle for inks, such as ultra-violet curableink and solid ink, which advantageously affects the holding pressure.

In embodiments, the coating disclosed herein comprises a SOF comprisinga plurality of segments, a plurality of linkers arranged as a covalentorganic framework (COF), such as a “solvent resistant” SOF, a cappedSOF, a composite SOF, and/or a periodic SOF. The term “solventresistant” refers, for example, to the substantial absence of (1) anyleaching out any atoms and/or molecules that were at one time part ofthe SOF and/or SOF composition (such as a composite SOF), and/or (2) anyphase separation of any molecules that were at one time part of the SOFand/or SOF composition (such as a composite SOF), that increases thesusceptibility of the layer into which the SOF is incorporated tosolvent/stress cracking or degradation. The term “substantial absence”refers for example, to less than about 0.5% of the atoms and/ormolecules of the SOF being leached out after continuously exposing orimmersing the SOF comprising imaging member (or SOF imaging memberlayer) to a liquid developer or solvent (such as, for example, eitheraqueous carrier fluid, or organic carrier fluid, such as isoparaffinichydrocarbons e.g. isopar) for a period of about 24 hours or longer (suchas about 48 hours, or about 72 hours), such as less than about 0.1% ofthe atoms and/or molecules of the SOF being leached out after exposingor immersing the SOF comprising imaging member (or SOF imaging memberlayer) to a liquid developer or solvent for a period of about 24 hoursor longer (such as about 48 hours, or about 72 hours), or less thanabout 0.01% of the atoms and/or molecules of the SOF being leached outafter exposing or immersing the SOF comprising imaging member (or SOFimaging member layer) to a liquid developer or solvent for a period ofabout 24 hours or longer (such as about 48 hours, or about 72 hours).

The term “organic carrier fluid” refers, for example, to organic liquidsor solvents employed in liquid developers and/or inks, which mayinclude, for example, alkenes, such as, for example, straight chainaliphatic hydrocarbons, branched chain aliphatic hydrocarbons, and thelike, such as where the straight or branched chain aliphatichydrocarbons have from about 1 to about 30 carbon atoms, such as fromabout 4 to about 20 carbons; aromatics, such as, for example, toluene,xylenes (such as o-, m-, p-xylene), and the like and/or mixturesthereof; isopar solvents or isoparaffinic hydrocarbons, such as anon-polar liquid of the ISOPAR™ series, such as ISOPAR E, ISOPAR G,ISOPAR H, ISOPAR L and ISOPAR M (manufactured by the Exxon Corporation,these hydrocarbon liquids are considered narrow portions ofisoparaffinic hydrocarbon fractions), the NORPAR™ series of liquids,which are compositions of n-paraffins available from Exxon Corporation,the SOLTROL™ series of liquids available from the Phillips PetroleumCompany, and the SHELLSOL™ series of liquids available from the ShellOil Company, or isoparaffinic hydrocarbon solvents having from about 10to about 18 carbon atoms, and or mixtures thereof. In embodiments, theorganic carrier fluid may be a mixture of one or more solvents, i.e., asolvent system, if desired. In addition, more polar solvents may also beused, if desired. Examples of more polar solvents that may be usedinclude halogenated and nonhalogenated solvents, such astetrahydrofuran, trichloro- and tetrachloroethane, dichloromethane,chloroform, monochlorobenzene, acetone, methanol, ethanol, benzene,ethyl acetate, dimethylformamide, cyclohexanone, N-methyl acetamide andthe like. The solvent may be composed of one, two, three or moredifferent solvents and/or and other various mixtures of theabove-mentioned solvents.

When a capping unit is introduced into the SOF, the SOF framework islocally ‘interrupted’ where the capping units are present. These SOFcompositions are ‘covalently doped’ because a foreign molecule is bondedto the SOF framework when capping units are present. Capped SOFcompositions may alter the properties of SOFs without changingconstituent building blocks. For example, the mechanical and physicalproperties of the capped SOF where the SOF framework is interrupted maydiffer from that of an uncapped SOF.

The SOFs of the present disclosure may be, at the macroscopic level,substantially pinhole-free SOFs or pinhole-free SOFs having continuouscovalent organic frameworks that can extend over larger length scalessuch as for instance much greater than a millimeter to lengths such as ameter and, in theory, as much as hundreds of meters. It will also beappreciated that SOFs tend to have large aspect ratios where typicallytwo dimensions of a SOF will be much larger than the third. SOFs havemarkedly fewer macroscopic edges and disconnected external surfaces thana collection of COF particles.

In embodiments, a “substantially pinhole-free SOF” or “pinhole-free SOF”may be formed from a reaction mixture deposited on the surface of anunderlying substrate. The term “substantially pinhole-free SOF” refers,for example, to an SOF that may or may not be removed from theunderlying substrate on which it was formed and contains substantiallyno pinholes, pores or gaps greater than the distance between the coresof two adjacent segments per square cm; such as, for example, less than10 pinholes, pores or gaps greater than about 250 nanometers in diameterper cm², or less than 5 pinholes, pores or gaps greater than about 100nanometers in diameter per cm². The term “pinhole-free SOF” refers, forexample, to an SOF that may or may not be removed from the underlyingsubstrate on which it was formed and contains no pinholes, pores or gapsgreater than the distance between the cores of two adjacent segments permicron², such as no pinholes, pores or gaps greater than about 500Angstroms in diameter per micron², or no pinholes, pores or gaps greaterthan about 250 Angstroms in diameter per micron², or no pinholes, poresor gaps greater than about 100 Angstroms in diameter per micron².

A description of various exemplary molecular building blocks, linkers,SOF types, capping groups, strategies to synthesize a specific SOF typewith exemplary chemical structures, building blocks whose symmetricalelements are outlined, and classes of exemplary molecular entities andexamples of members of each class that may serve as molecular buildingblocks for SOFs are detailed in U.S. patent application Ser. Nos.12/716,524; 12/716,449; 12/716,706; 12/716,324; 12/716,686; 12/716,571;12/815,688; 12/845,053; 12/845,235; 12/854,962; 12/854,957; and12/845,052 entitled “Structured Organic Films,” “Structured OrganicFilms Having an Added Functionality,” “Mixed Solvent Process forPreparing Structured Organic Films,” “Composite Structured OrganicFilms,” “Process For Preparing Structured Organic Films (SOFs) Via aPre-SOF,” “Electronic Devices Comprising Structured Organic Films,”“Periodic Structured Organic Films,” “Capped Structured Organic FilmCompositions,” “Imaging Members Comprising Capped Structured OrganicFilm Compositions,” “Imaging Members for Ink-Based Digital PrintingComprising Structured Organic Films,” “Imaging Devices ComprisingStructured Organic Films,” and “Imaging Members Comprising StructuredOrganic Films,” respectively; and U.S. Provisional Application No.61/157,411, entitled “Structured Organic Films” filed Mar. 4, 2009, thedisclosures of which are totally incorporated herein by reference intheir entireties.

Molecular Building Block

The SOFs of the present disclosure comprise molecular building blockshaving a segment (5) and functional groups (Fg). Molecular buildingblocks require at least two functional groups (x≧2) and may comprise asingle type or two or more types of functional groups. Functional groupsare the reactive chemical moieties of molecular building blocks thatparticipate in a chemical reaction to link together segments during theSOF forming process. A segment is the portion of the molecular buildingblock that supports functional groups and comprises all atoms that arenot associated with functional groups. Further, the composition of amolecular building block segment remains unchanged after SOF formation.

Molecular Building Block Symmetry

Molecular building block symmetry relates to the positioning offunctional groups (Fgs) around the periphery of the molecular buildingblock segments. Without being bound by chemical or mathematical theory,a symmetric molecular building block is one where positioning of Fgs maybe associated with the ends of a rod, vertexes of a regular geometricshape, or the vertexes of a distorted rod or distorted geometric shape.For example, the most symmetric option for molecular building blockscontaining four Fgs are those whose Fgs overlay with the corners of asquare or the apexes of a tetrahedron.

Use of symmetrical building blocks is practiced in embodiments of thepresent disclosure for two reasons: (1) the patterning of molecularbuilding blocks may be better anticipated because the linking of regularshapes is a better understood process in reticular chemistry, and (2)the complete reaction between molecular building blocks is facilitatedbecause for less symmetric building blocks errantconformations/orientations may be adopted which can possibly initiatenumerous linking defects within SOFs.

FIGS. 4A-O illustrate exemplary building blocks whose symmetricalelements are outlined. Such symmetrical elements are found in buildingblocks that may be used in the present disclosure.

Non-limiting examples of various classes of exemplary molecular entitiesthat may serve as molecular building blocks for SOFs of the presentdisclosure include building blocks containing a carbon or silicon atomiccore; building blocks containing alkoxy cores; building blockscontaining a nitrogen or phosphorous atomic core; building blockscontaining aryl cores; building blocks containing carbonate cores;building blocks containing carbocyclic-, carbobicyclic-, orcarbotricyclic core; and building blocks containing an oligothiophenecore.

In embodiments, the Type 1 SOF contains segments, which are not locatedat the edges of the SOF, that are connected by linkers to at least threeother segments. For example, in embodiments the SOF comprises at leastone symmetrical building block selected from the group consisting ofideal triangular building blocks, distorted triangular building blocks,ideal tetrahedral building blocks, distorted tetrahedral buildingblocks, ideal square building blocks, and distorted square buildingblocks.

In embodiments, Type 2 and 3 SOF contains at least one segment type,which are not located at the edges of the SOF, that are connected bylinkers to at least three other segments. For example, in embodimentsthe SOF comprises at least one symmetrical building block selected fromthe group consisting of ideal triangular building blocks, distortedtriangular building blocks, ideal tetrahedral building blocks, distortedtetrahedral building blocks, ideal square building blocks, and distortedsquare building blocks.

Functional Group

Functional groups are the reactive chemical moieties of molecularbuilding blocks that participate in a chemical reaction to link togethersegments during the SOF forming process. Functional groups may becomposed of a single atom, or functional groups may be composed of morethan one atom. The atomic compositions of functional groups are thosecompositions normally associated with reactive moieties in chemicalcompounds. Non-limiting examples of functional groups include halogens,alcohols, ethers, ketones, carboxylic acids, esters, carbonates, amines,amides, imines, ureas, aldehydes, isocyanates, tosylates, alkenes,alkynes and the like.

Molecular building blocks contain a plurality of chemical moieties, butonly a subset of these chemical moieties are intended to be functionalgroups during the SOF forming process. Whether or not a chemical moietyis considered a functional group depends on the reaction conditionsselected for the SOF forming process. Functional groups (Fg) denote achemical moiety that is a reactive moiety, that is, a functional groupduring the SOF forming process.

In the SOF forming process, the composition of a functional group willbe altered through the loss of atoms, the gain of atoms, or both theloss and the gain of atoms; or, the functional group may be lostaltogether. In the SOF, atoms previously associated with functionalgroups become associated with linker groups, which are the chemicalmoieties that join together segments. Functional groups havecharacteristic chemistries and those of ordinary skill in the art cangenerally recognize in the present molecular building blocks the atom(s)that constitute functional group(s). It should be noted that an atom orgrouping of atoms that are identified as part of the molecular buildingblock functional group may be preserved in the linker group of the SOF.Linker groups are described below.

Capping Unit

Capping units of the present disclosure are molecules that ‘interrupt’the regular network of covalently bonded building blocks normallypresent in an SOF. Capped SOF compositions are tunable materials whoseproperties can be varied through the type and amount of capping unitintroduced. Capping units may comprise a single type or two or moretypes of functional groups and/or chemical moieties.

In embodiments, the SOF comprises a plurality of segments, where allsegments have an identical structure, and a plurality of linkers, whichmay or may not have an identical structure, wherein the segments thatare not at the edges of the SOF are connected by linkers to at leastthree other segments and/or capping groups. In embodiments, the SOFcomprises a plurality of segments where the plurality of segmentscomprises at least a first and a second segment that are different instructure, and the first segment is connected by linkers to at leastthree other segments and/or capping groups when it is not at the edge ofthe SOF.

In embodiments, the SOF comprises a plurality of linkers including atleast a first and a second linker that are different in structure, andthe plurality of segments either comprises at least a first and a secondsegment that are different in structure, where the first segment, whennot at the edge of the SOF, is connected to at least three othersegments and/or capping groups, wherein at least one of the connectionsis via the first linker, and at least one of the connections is via thesecond linker; or comprises segments that all have an identicalstructure, and the segments that are not at the edges of the SOF areconnected by linkers to at least three other segments and/or cappinggroups, wherein at least one of the connections is via the first linker,and at least one of the connections is via the second linker.

Segment

A segment is the portion of the molecular building block that supportsfunctional groups and comprises all atoms that are not associated withfunctional groups. Further, the composition of a molecular buildingblock segment remains unchanged after SOF formation. In embodiments, theSOF may contain a first segment having a structure the same as ordifferent from a second segment. In other embodiments, the structures ofthe first and/or second segments may be the same as or different from athird segment, forth segment, fifth segment, etc. A segment is also theportion of the molecular building block that can provide an inclinedproperty. Inclined properties are described later in the embodiments.

In specific embodiments, the segment of the SOF comprises at least oneatom of an element that is not carbon, such at least one atom selectedfrom the group consisting of hydrogen, oxygen, nitrogen, silicon,phosphorous, selenium, fluorine, boron, and sulfur.

Linker

A linker is a chemical moiety that emerges in a SOF upon chemicalreaction between functional groups present on the molecular buildingblocks and/or capping unit.

A linker may comprise a covalent bond, a single atom, or a group ofcovalently bonded atoms. The former is defined as a covalent bond linkerand may be, for example, a single covalent bond or a double covalentbond and emerges when functional groups on all partnered building blocksare lost entirely. The latter linker type is defined as a chemicalmoiety linker and may comprise one or more atoms bonded together bysingle covalent bonds, double covalent bonds, or combinations of thetwo. Atoms contained in linking groups originate from atoms present infunctional groups on molecular building blocks prior to the SOF formingprocess. Chemical moiety linkers may be well-known chemical groups suchas, for example, esters, ketones, amides, imines, ethers, urethanes,carbonates, and the like, or derivatives thereof.

For example, when two hydroxyl (—OH) functional groups are used toconnect segments in a SOF via an oxygen atom, the linker would be theoxygen atom, which may also be described as an ether linker. Inembodiments, the SOF may contain a first linker having a structure thesame as or different from a second linker. In other embodiments, thestructures of the first and/or second linkers may be the same as ordifferent from a third linker, etc.

Metrical Parameters of SOFs

SOFs have any suitable aspect ratio. In embodiments, SOFs have aspectratios for instance greater than about 30:1 or greater than about 50:1,or greater than about 70:1, or greater than about 100:1, such as about1000:1. The aspect ratio of a SOF is defined as the ratio of its averagewidth or diameter (that is, the dimension next largest to its thickness)to its average thickness (that is, its shortest dimension). The term‘aspect ratio,’ as used here, is not bound by theory. The longestdimension of a SOF is its length and it is not considered in thecalculation of SOF aspect ratio.

Multilayer SOFs

A SOF may comprise a single layer or a plurality of layers (that is,two, three or more layers). SOFs that are comprised of a plurality oflayers may be physically joined (e.g., dipole and hydrogen bond) orchemically joined. Physically attached layers are characterized byweaker interlayer interactions or adhesion; therefore physicallyattached layers may be susceptible to delamination from each other.Chemically attached layers are expected to have chemical bonds (e.g.,covalent or ionic bonds) or have numerous physical or intermolecular(supramolecular) entanglements that strongly link adjacent layers.

Therefore, delamination of chemically attached layers is much moredifficult. Chemical attachments between layers may be detected usingspectroscopic methods such as focusing infrared or Raman spectroscopy,or with other methods having spatial resolution that can detect chemicalspecies precisely at interfaces. In cases where chemical attachmentsbetween layers are different chemical species than those within thelayers themselves it is possible to detect these attachments withsensitive bulk analyses such as solid-state nuclear magnetic resonancespectroscopy or by using other bulk analytical methods.

In the embodiments, the coating may comprise a SOF where the SOF may bea single layer (mono-segment thick or multi-segment thick) or multiplelayers (each layer being mono-segment thick or multi-segment thick).“Thickness” refers, for example, to the smallest dimension of the film.As discussed above, in a SOF, segments are molecular units that arecovalently bonded through linkers to generate the molecular framework ofthe film. The thickness of the film may also be defined in terms of thenumber of segments that is counted along that axis of the film whenviewing the cross-section of the film. A “monolayer” SOF is the simplestcase and refers, for example, to where a film is one segment thick. ASOF where two or more segments exist along this axis is referred to as a“multi-segment” thick SOF.

An exemplary method for preparing coating comprising a physicallyattached multilayer SOFs includes: (1) forming a base SOF layer that maybe cured by a first curing cycle, and (2) forming upon the base layer asecond reactive wet layer followed by a second curing cycle and, ifdesired, repeating the second step to form a third layer, a forth layerand so on. The physically stacked multilayer SOFs may have thicknessesgreater than about 20 Angstroms such as, for example, the followingillustrative thicknesses: about 20 Angstroms to about 10 cm, such asabout 1 nm to about 10 mm, or about 0.1 mm Angstroms to about 5 mm. Inprinciple there is no limit with this process to the number of layersthat may be physically stacked.

In embodiments, a coating comprising a multilayer SOF may be formed by amethod for preparing chemically attached multilayer SOFs by: (1) forminga base SOF layer having functional groups present on the surface (ordangling functional groups) from a first reactive wet layer, and (2)forming upon the base layer a second SOF layer from a second reactivewet layer that comprises molecular building blocks with functionalgroups capable of reacting with the dangling functional groups on thesurface of the base SOF layer. In further embodiments, a capped. SOF mayserve as the base layer in which the functional groups present that werenot suitable or complementary to participate in the specific chemicalreaction to link together segments during the base layer SOF formingprocess may be available for reacting with the molecular building blocksof the second layer to from an chemically bonded multilayer SOF. Ifdesired, the formulation used to form the second SOF layer shouldcomprise molecular building blocks with functional groups capable ofreacting with the functional groups from the base layer as well asadditional functional groups that will allow for a third layer to bechemically attached to the second layer. The chemically stackedmultilayer SOFs may have thicknesses greater than about 20 Angstromssuch as, for example, the following illustrative thicknesses: about 20Angstroms to about 10 cm, such as about 1 nm to about 10 mm, or about0.1 mm Angstroms to about 5 mm. In principle there is no limit with thisprocess to the number of layers that may be chemically stacked.

In embodiments, the method for preparing chemically attached multilayerSOFs comprises promoting chemical attachment of a second SOF onto anexisting SOF (base layer) by using a small excess of one molecularbuilding block (when more than one molecular building block is present)during the process used to form the SOF (base layer) whereby thefunctional groups present on this molecular building block will bepresent on the base layer surface. The surface of base layer may betreated with an agent to enhance the reactivity of the functional groupsor to create an increased number of functional groups.

In an embodiment the dangling functional groups or chemical moietiespresent on the surface of an SOF or capped SOF may be altered toincrease the propensity for covalent attachment (or, alternatively, todisfavor covalent attachment) of particular classes of molecules orindividual molecules, such as SOFs, to a base layer or any additionalsubstrate or SOF layer. For example, the surface of a base layer, suchas an SOF layer, which may contain reactive dangling functional groups,may be rendered pacified through surface treatment with a cappingchemical group. For example, a SOF layer having dangling hydroxylalcohol groups may be pacified by treatment with trimethylsiylchloridethereby capping hydroxyl groups as stable trimethylsilylethers.Alternatively, the surface of base layer may be treated with anon-chemically bonding agent, such as a wax, to block reaction withdangling functional groups from subsequent layers.

Molecular Building Block Symmetry

Molecular building block symmetry relates to the positioning offunctional groups (Fgs) around the periphery of the molecular buildingblock segments. Without being bound by chemical or mathematical theory,a symmetric molecular building block is one where positioning of Fgs maybe associated with the ends of a rod, vertexes of a regular geometricshape, or the vertexes of a distorted rod or distorted geometric shape.For example, the most symmetric option for molecular building blockscontaining four Fgs are those whose Fgs overlay with the corners of asquare or the apexes of a tetrahedron.

Use of symmetrical building blocks is practiced in embodiments of thepresent disclosure for two reasons: (1) the patterning of molecularbuilding blocks may be better anticipated because the linking of regularshapes is a better understood process in reticular chemistry, and (2)the complete reaction between molecular building blocks is facilitatedbecause for less symmetric building blocks errantconformations/orientations may be adopted which can possibly initiatenumerous linking defects within SOFs.

In embodiments, a Type 1 SOF contains segments, which are not located atthe edges of the SOF, that are connected by linkers to at least threeother segments. For example, in embodiments the SOF comprises at leastone symmetrical building block selected from the group consisting ofideal triangular building blocks, distorted triangular building blocks,ideal tetrahedral building blocks, distorted tetrahedral buildingblocks, ideal square building blocks, and distorted square buildingblocks. In embodiments, Type 2 and 3 SOF contains at least one segmenttype, which are not located at the edges of the SOF, that are connectedby linkers to at least three other segments. For example, in embodimentsthe SOF comprises at least one symmetrical building block selected fromthe group consisting of ideal triangular building blocks, distortedtriangular building blocks, ideal tetrahedral building blocks, distortedtetrahedral building blocks, ideal square building blocks, and distortedsquare building blocks.

Practice of Linking Chemistry

In embodiments linking chemistry may occur wherein the reaction betweenfunctional groups produces a volatile byproduct that may be largelyevaporated or expunged from the SOF during or after the film formingprocess or wherein no byproduct is formed. Linking chemistry may beselected to achieve a SOF for applications where the presence of linkingchemistry byproducts is not desired. Linking chemistry reactions mayinclude, for example, condensation, addition/elimination, and additionreactions, such as, for example, those that produce esters, imines,ethers, carbonates, urethanes, amides, acetals, and silyl ethers.

In embodiments the linking chemistry via a reaction between functiongroups producing a non-volatile byproduct that largely remainsincorporated within the SOF after the film forming process. Linkingchemistry in embodiments may be selected to achieve a SOF forapplications where the presence of linking chemistry byproducts does notimpact the properties or for applications where the presence of linkingchemistry byproducts may alter the properties of a SOF (such as, forexample, the electroactive, hydrophobic or hydrophilic nature of theSOF). Linking chemistry reactions may include, for example,substitution, metathesis, and metal catalyzed coupling reactions, suchas those that produce carbon-carbon bonds.

For all linking chemistry the ability to control the rate and extent ofreaction between building blocks via the chemistry between buildingblock functional groups is an important aspect of the presentdisclosure. Reasons for controlling the rate and extent of reaction mayinclude adapting the film forming process for different coating methodsand tuning the microscopic arrangement of building blocks to achieve aperiodic SOF, as defined in earlier embodiments.

Innate Properties of COFs

COFs have innate properties such as high thermal stability (typicallyhigher than 400° C. under atmospheric conditions); poor solubility inorganic solvents (chemical stability), and porosity (capable ofreversible guest uptake). In embodiments, SOFs may also possess theseinnate properties.

Added Functionality of SOFs

Added functionality denotes a property that is not inherent toconventional COFs and may occur by the selection of molecular buildingblocks wherein the molecular compositions provide the addedfunctionality in the resultant SOF. Added functionality may arise uponassembly of molecular building blocks having an “inclined property” forthat added functionality. Added functionality may also arise uponassembly of molecular building blocks having no “inclined property” forthat added functionality but the resulting SOF has the addedfunctionality as a consequence of linking segments (S) and linkers intoa SOF. Furthermore, emergence of added functionality may arise from thecombined effect of using molecular building blocks bearing an “inclinedproperty” for that added functionality whose inclined property ismodified or enhanced upon linking together the segments and linkers intoa SOF.

An Inclined Property of a Molecular Building Block

The term “inclined property” of a molecular building block refers, forexample, to a property known to exist for certain molecular compositionsor a property that is reasonably identifiable by a person skilled in artupon inspection of the molecular composition of a segment. As usedherein, the terms “inclined property” and “added functionality” refer tothe same general property (e.g., hydrophobic, electroactive, etc.) but“inclined property” is used in the context of the molecular buildingblock and “added functionality” is used in the context of the SOF.

The hydrophobic (superhydrophobic), hydrophilic, lipophobic(superlipophobic), lipophilic, photochromic and/or electroactive(conductor, semiconductor, charge transport material) nature of an SOFare some examples of the properties that may represent an “addedfunctionality” of an SOF. These and other added functionalities mayarise from the inclined properties of the molecular building blocks ormay arise from building blocks that do not have the respective addedfunctionality that is observed in the SOF.

The term hydrophobic (superhydrophobic) refers, for example, to theproperty of repelling water, or other polar species, such as methanol,it also means an inability to absorb water and/or to swell as a result.Furthermore, hydrophobic implies an inability to form strong hydrogenbonds to water or other hydrogen bonding species. Hydrophobic materialsare typically characterized by having water contact angles greater than90° as measured using a contact angle goniometer or related device.Highly hydrophobic as used herein can be described as when a droplet ofwater forms a high contact angle with a surface, such as a contact angleof from about 130° to about 180°. Superhydrophobic as used herein can bedescribed as when a droplet of water forms a high contact angle with asurface, such as a contact angle of greater than about 150°, or fromgreater about 150° to about 180°.

Superhydrophobic as used herein can be described as when a droplet ofwater forms a sliding angle with a surface, such as a sliding angle offrom about 1′ to less than about 30°, or from about 1° to about 25°, ora sliding angle of less than about 15°, or a sliding angle of less thanabout 10°.

The term hydrophilic refers, for example, to the property of attracting,adsorbing, or absorbing water or other polar species, or a surface.Hydrophilicity may also be characterized by swelling of a material bywater or other polar species, or a material that can diffuse ortransport water, or other polar species, through itself. Hydrophilicity,is further characterized by being able to form strong or numeroushydrogen bonds to water or other hydrogen bonding species.

The term lipophobic (oleophobic) refers, for example, to the property ofrepelling oil or other non-polar species such as alkanes, fats, andwaxes. Lipophobic materials are typically characterized by having oilcontact angles greater than 90° as measured using a contact anglegoniometer or related device. In the present disclosure, the termoleophobic refers, for example, to wettability of a surface that has anoil contact angle of approximately about 55° or greater, for example,with UV curable ink, solid ink, hexadecane, dodecane, hydrocarbons, etc.Highly oleophobic as used herein can be described as when a droplet ofhydrocarbon-based liquid, for example, hexadecane or ink, forms a highcontact angle with a surface, such as a contact angle of from about 130°or greater than about 130° to about 175° or from about 135° to about170°. Superoleophobic as used herein can be described as when a dropletof hydrocarbon-based liquid, for example, ink, forms a highcontact-angle with a surface, such as a contact angle that is greaterthan 150°, or from greater than about 150° to about 175°, or fromgreater than about 150° to about 160°.

Superoleophobic as used herein can also be described as when a dropletof a hydrocarbon-based liquid, for example, hexadecane, forms a slidingangle with a surface of from about 1° to less than about 30°, or fromabout 1° to less than about 25°, or a sliding angle of less than about25°, or a sliding angle of less than about 15°, or a sliding angle ofless than about 10°.

The term lipophilic (oleophilic) refers, for example, to the propertyattracting oil or other non-polar species such as alkanes, fats, andwaxes or a surface that is easily wetted by such species. Lipophilicmaterials are typically characterized by having a low to nil oil contactangle as measured using, for example, a contact angle goniometer.Lipophilicity can also be characterized by swelling of a material byhexane or other non-polar liquids.

SOFs with hydrophobic added functionality may be prepared by usingmolecular building blocks with inclined hydrophobic properties and/orhave a rough, textured, or porous surface on the sub-micron to micronscale. A paper describing materials having a rough, textured, or poroussurface on the sub-micron to micron scale being hydrophobic was authoredby Cassie and Baxter (Cassie, A. B. D.; Baxter, S. Trans. Faraday Soc.,1944, 40, 546).

Molecular building blocks comprising or bearing highly-fluorinatedsegments have inclined hydrophobic properties and may lead to SOFs withhydrophobic added functionality. Highly-fluorinated segments are definedas the number of fluorine atoms present on the segment(s) divided by thenumber of hydrogen atoms present on the segment(s) being greater thanone. Fluorinated segments, which are not highly-fluorinated segments mayalso lead to SOFs with hydrophobic added functionality.

The fluorinated SOFs of the present disclosure may be made from versionsof any of the molecular building blocks, segments, and/or linkerswherein one or more hydrogen(s) in the molecular building blocks arereplaced with fluorine. The above-mentioned fluorinated segments mayinclude, for example, tetrafluorohydroquinone, perfluoroadipic acidhydrate, 4,4′-(hexafluoroisopropylidene)diphthalic anhydride,4,4′-(hexafluoroisopropylidene)diphenol, and the like. Other exemplaryfluorinated SOFs are described in U.S. patent application Ser. No.13/173,948, now U.S. Pat. No. 8,247,142, to Adrien P. Cote and MatthewA. Heuft entitled “Fluorinated Structured Organic Film Compositions,”which is being filed concurrently with the present application, thedisclosure of which is totally incorporated herein by reference in itsentirety.

SOFs having a rough, textured, or porous surface on the sub-micron tomicron scale may also be hydrophobic. The rough, textured, or porous SOFsurface can result from dangling functional groups present on the filmsurface or from the structure of the SOF. The type of pattern and degreeof patterning depends on the geometry of the molecular building blocksand the linking chemistry efficiency. The feature size that leads tosurface roughness or texture is from about 100 nm to about 10 μm, suchas from about 500 nm to about 5 μm.

SOFs with hydrophilic added functionality may be prepared by usingmolecular building blocks with inclined hydrophilic properties and/orcomprising polar linking groups. hydrophilic added functionality. Theterm polar substituents refers, for example, to substituents that canform hydrogen bonds with water and include, for example, hydroxyl,amino, ammonium, and carbonyl (such as ketone, carboxylic acid, ester,amide, carbonate, urea).

SOFs with electroactive added functionality may be prepared by usingmolecular building blocks with inclined electroactive properties and/orbe electroactive resulting from the assembly of conjugated segments andlinkers. The following sections describe molecular building blocks withinclined hole transport properties, inclined electron transportproperties, and inclined semiconductor properties.

Process for Preparing a Structured Organic Film

The process for making SOFs to be included in the coatings of thepresent disclosure, such as solvent resistant SOFs, typically comprisesa number of activities or steps (set forth below) that may be performedin any suitable sequence or where two or more activities are performedsimultaneously or in close proximity in time:

A process for preparing a structured organic film comprising:

(a) preparing a liquid-containing reaction mixture comprising aplurality of molecular building blocks each comprising a segment and anumber of functional groups, and a pre-SOF;

(b) depositing the reaction mixture as a wet film;

(c) promoting a change of the wet film including the molecular buildingblocks to a dry film comprising the SOF comprising a plurality of thesegments and a plurality of linkers arranged as a covalent organicframework, wherein at a macroscopic level the covalent organic frameworkis a film;

(d) optionally removing the SOF from the coating substrate to obtain afree-standing SOF;

(e) optionally processing the free-standing SOF into a roll;

(f) optionally cutting and seaming the SOF into a belt; and

(e) optionally processing the free-standing SOF into a roll;

(f) optionally cutting and seaming the SOF into a belt; and

(g) optionally performing the above SOF formation process(es) upon anSOF

(which was prepared by the above SOF formation process(es)) as asubstrate for subsequent SOF formation process(es).

The process for making capped SOFs and/or composite SOFs typicallycomprises a similar number of activities or steps (set forth above) thatare used to make a non-capped SOF. The capping unit and/or secondarycomponent may be added during either step a, b or c, depending thedesired distribution of the capping unit in the resulting SOF. Forexample, if it is desired that the capping unit and/or secondarycomponent distribution is substantially uniform over the resulting SOF,the capping unit may be added during step a. Alternatively, if, forexample, a more heterogeneous distribution of the capping unit and/orsecondary component is desired, adding the capping unit and/or secondarycomponent (such as by spraying it on the film formed during step b orduring the promotion step of step c) may occur during steps b and c.

The above activities or steps may be conducted at atmospheric, superatmospheric, or subatmospheric pressure. The term “atmospheric pressure”as used herein refers to a pressure of about 760 torr. The term “superatmospheric” refers to pressures greater than atmospheric pressure, butless than 20 atm. The term “subatmospheric pressure” refers to pressuresless than atmospheric pressure. In an embodiment, the activities orsteps may be conducted at or near atmospheric pressure. Generally,pressures of from about 0.1 atm to about 2 atm, such as from about 0.5atm to about 1.5 atm, or 0.8 atm to about 1.2 atm may be convenientlyemployed.

Process Action A: Preparation of the Liquid-Containing Reaction Mixture

The reaction mixture comprises a plurality of molecular building blocksthat are dissolved, suspended, or mixed in a liquid. The plurality ofmolecular building blocks may be of one type or two or more types. Whenone or more of the molecular building blocks is a liquid, the use of anadditional liquid is optional. Catalysts may optionally be added to thereaction mixture to enable pre-SOF formation and/or modify the kineticsof SOF formation during Action C described above. The term “pre-SOF” mayrefer to, for example, at least two molecular building blocks that havereacted and have a molecular weight higher than the starting molecularbuilding block and contain multiple functional groups capable ofundergoing further reactions with functional groups of other buildingblocks or pre-SOFs to obtain a SOF, which may be a substantiallydefect-free or defect-free SOF, and/or the ‘activation’ of molecularbuilding block functional groups that imparts enhanced or modifiedreactivity for the film forming process. Activation may includedissociation of a functional group moiety, pre-association with acatalyst, association with a solvent molecule, liquid, second solvent,second liquid, secondary component, or with any entity that modifiesfunctional group reactivity. In embodiments, pre-SOF formation mayinclude the reaction between molecular building blocks or the‘activation’ of molecular building block functional groups, or acombination of the two. The formation of the “pre-SOF” may be achievedby in a number of ways, such as heating the reaction mixture, exposureof the reaction mixture to UV radiation, or any other means of partiallyreacting the molecular building blocks and/or activating functionalgroups in the reaction mixture prior to deposition of the wet layer onthe substrate. Additives or secondary components may optionally be addedto the reaction mixture to alter the physical properties of theresulting SOF.

The reaction mixture components (molecular building blocks, optionally aliquid, optionally catalysts, and optionally additives) are combined ina vessel. The order of addition of the reaction mixture components mayvary; however, typically when a process for preparing a SOF includes apre-SOF or formation of a pre-SOF, the catalyst, when present, may beadded to the reaction mixture before depositing the reaction mixture asa wet film. In embodiments, the molecular building blocks may be reactedactinically, thermally, chemically or by any other means with or withoutthe presence of a catalyst to obtain a pre-SOF. The pre-SOF and themolecular building blocks formed in the absence of catalyst may be maybe heated in the liquid in the absence of the catalyst to aid thedissolution of the molecular building blocks and pre-SOFs. Inembodiments, the pre-SOF and the molecular building blocks formed in thepresence of catalyst may be may be heated at a temperature that does notcause significant further reaction of the molecular building blocksand/or the pre-SOFs to aid the dissolution of the molecular buildingblocks and pre-SOFs. The reaction mixture may also be mixed, stirred,milled, or the like, to ensure even distribution of the formulationcomponents prior to depositing the reaction mixture as a wet film.

In embodiments, the reaction mixture may be heated prior to beingdeposited as a wet film. This may aid the dissolution of one or more ofthe molecular building blocks and/or increase the viscosity of thereaction mixture by the partial reaction of the reaction mixture priorto depositing the wet layer to form pre-SOFs. For example, the weightpercent of molecular building blocks in the reaction mixture that areincorporated into pre-reacted molecular building blocks pre-SOFs may beless than 20%, such as about 15% to about 1%, or 10% to about 5%. Inembodiments, the molecular weight of the 95% pre-SOF molecules is lessthan 5,000 daltons, such as 2,500 daltons, or 1,000 daltons. Thepreparation of pre-SOFs may be used to increase the loading of themolecular building blocks in the reaction mixture.

In the case of pre-SOF formation via functional group activation, themolar percentage of functional groups that are activated may be lessthan 50%, such as about 30% to about 10%, or about 10% to about 5%.

In embodiments, the two methods of pre-SOF formation (pre-SOF formationby the reaction between molecular building blocks or pre-SOF formationby the ‘activation’ of molecular building block functional groups) mayoccur in combination and the molecular building blocks incorporated intopre-SOF structures may contain activated functional groups. Inembodiments, pre-SOF formation by the reaction between molecularbuilding blocks and pre-SOF formation by the ‘activation’ of molecularbuilding block functional groups may occur simultaneously.

In embodiments, the duration of pre-SOF formation lasts about 10 secondsto about 48 hours, such as about 30 seconds to about 12 hours, or about1 minute to 6 hours.

In particular embodiments, the reaction mixture needs to have aviscosity that will support the deposited wet layer. Reaction mixtureviscosities range from about 10 to about 50,000 cps, such as from about25 to about 25,000 cps or from about 50 to about 1000 cps.

The molecular building block and capping unit loading or “loading” inthe reaction mixture is defined as the total weight of the molecularbuilding blocks and optionally the capping units and catalysts dividedby the total weight of the reaction mixture. Building block loadings mayrange from about 3 to 100%, such as from about 5 to about 50%, or fromabout 15 to about 40%. In the case where a liquid molecular buildingblock is used as the only liquid component of the reaction mixture (i.e.no additional liquid is used), the building block loading would be about100%. The capping unit loading may be chosen, so as to achieve thedesired loading of the capping group. For example, depending on when thecapping unit is to be added to the reaction mixture, capping unitloadings may range, by weight, from about 3 to 80%, such as from about 5to about 50%, or from about 15 to about 40% by weight.

In embodiments, the theoretical upper limit for capping unit loading isthe molar amount of capping units that reduces the number of availablelinking groups to 2 per molecular building block in the liquid SOFformulation. In such a loading, substantial SOF formation may beeffectively inhibited by exhausting (by reaction with the respectivecapping group) the number of available linkable functional groups permolecular building block. For example, in such a situation (where thecapping unit loading is in an amount sufficient to ensure that the molarexcess of available linking groups is less than 2 per molecular buildingblock in the liquid SOF formulation), oligomers, linear polymers, andmolecular building blocks that are fully capped with capping units maypredominately form instead of an SOF.

In embodiments, the pre-SOF may be made from building blocks with one ormore of the added functionality selected from the group consisting ofhydrophobic added functionality, superhydrophobic added functionality,hydrophilic added functionality, lipophobic added functionality,superlipophobic added functionality, lipophilic added functionality,photochromic added functionality, and electroactive added functionality.In embodiments, the inclined property of the molecular building blocksis the same as the added functionality of the pre-SOF. In embodiments,the added functionality of the SOF is not an inclined property of themolecular building blocks.

Liquids used in the reaction mixture may be pure liquids, such assolvents, and/or solvent mixtures. Liquids are used to dissolve orsuspend the molecular building blocks and catalyst/modifiers in thereaction mixture. Liquid selection is generally based on balancing thesolubility/dispersion of the molecular building blocks and a particularbuilding block loading, the viscosity of the reaction mixture, and theboiling point of the liquid, which impacts the promotion of the wetlayer to the dry SOF. Suitable liquids may have boiling points fromabout 30 to about 300° C., such as from about 65° C. to about 250° C.,or from about 100° C. to about 180° C.

Liquids may include molecule classes such as alkanes (hexane, heptane,octane, nonane, decane, cyclohexane, cycloheptane, cyclooctane,decalin); mixed alkanes (hexanes, heptanes); branched alkanes(isooctane); aromatic compounds (toluene, o-, m-, p-xylene, mesitylene,nitrobenzene, benzonitrile, butylbenzene, aniline); ethers (benzyl ethylether, butyl ether, isoamyl ether, propyl ether); cyclic ethers(tetrahydrofuran, dioxane), esters (ethyl acetate, butyl acetate, butylbutyrate, ethoxyethyl acetate, ethyl propionate, phenyl acetate, methylbenzoate); ketones (acetone, methyl ethyl ketone, methyl isobutylketone,diethyl ketone, chloroacetone, 2-heptanone), cyclic ketones(cyclopentanone, cyclohexanone), amines (1°, 2°, or 3° amines such asbutylamine, diisopropylamine, triethylamine, diisoproylethylamine;pyridine); amides (dimethylformamide, N-methylpyrrolidinone,N,N-dimethylformamide); alcohols (methanol, ethanol, n-, i-propanol, n-,i-, t-butanol, 1-methoxy-2-propanol, hexanol, cyclohexanol, 3-pentanol,benzyl alcohol); nitriles (acetonitrile, benzonitrile, butyronitrile),halogenated aromatics (chlorobenzene, dichlorobenzene,hexafluorobenzene), halogenated alkanes (dichloromethane, chloroform,dichloroethylene, tetrachloroethane); and water.

Mixed liquids comprising a first solvent, second solvent, third solvent,and so forth may also be used in the reaction mixture. Two or moreliquids may be used to aid the dissolution/dispersion of the molecularbuilding blocks; and/or increase the molecular building block loading;and/or allow a stable wet film to be deposited by aiding the wetting ofthe substrate and deposition instrument; and/or modulate the promotionof the wet layer to the dry SOF. In embodiments, the second solvent is asolvent whose boiling point or vapor-pressure curve or affinity for themolecular building blocks differs from that of the first solvent. Inembodiments, a first solvent has a boiling point higher than that of thesecond solvent. In embodiments, the second solvent has a boiling pointequal to or less than about 100° C., such as in the range of from about30° C. to about 100° C., or in the range of from about 40° C. to about90° C., or about 50° C. to about 80° C.

In embodiments, the first solvent, or higher boiling point solvent, hasa boiling point equal to or greater than about 65° C., such as in therange of from about 80° C. to about 300° C., or in the range of fromabout 100° C. to about 250° C., or about 100° C. to about 180° C. Thehigher boiling point solvent may include, for example, the following(the value in parentheses is the boiling point of the compound):hydrocarbon solvents such as amylbenzene (202° C.), isopropylbenzene(152° C.), 1,2-diethylbenzene (183° C.), 1,3-diethylbenzene (181° C.),1,4-diethylbenzene (184° C.), cyclohexylbenzene (239° C.), dipentene(177° C.), 2,6-dimethylnaphthalene (262° C.), p-cymene (177° C.),camphor oil (160-185° C.), solvent naphtha (110-200° C.), cis-decalin(196° C.), trans-decalin (187° C.), decane (174° C.), tetralin (207°C.), turpentine oil (153-175° C.), kerosene (200-245° C.), dodecane(216° C.), dodecylbenzene (branched), and so forth; ketone and aldehydesolvents such as acetophenone (201.7° C.), isophorone (215.3° C.),phorone (198-199° C.), methylcyclohexanone (169.0-170.5° C.), methyln-heptyl ketone (195.3° C.), and so forth; ester solvents such asdiethyl phthalate (296.1° C.), benzyl acetate (215.5° C.),γ-butyrolactone (204° C.), dibutyl oxalate (240° C.), 2-ethylhexylacetate (198.6° C.), ethyl benzoate (213.2° C.), benzyl formate (203°C.), and so forth; diethyl sulfate (208° C.), sulfolane (285° C.), andhalohydrocarbon solvents; etherified hydrocarbon solvents; alcoholsolvents; ether/acetal solvents; polyhydric alcohol solvents; carboxylicanhydride solvents; phenolic solvents; water; and silicone solvents.

The ratio of the mixed liquids may be established by one skilled in theart. The ratio of liquids a binary mixed liquid may be from about 1:1 toabout 99:1, such as from about 1:10 to about 10:1, or about 1:5 to about5:1, by volume. When n liquids are used, with n ranging from about 3 toabout 6, the amount of each liquid ranges from about 1% to about 95%such that the sum of each liquid contribution equals 100%.

In embodiments, the mixed liquid comprises at least a first and a secondsolvent with different boiling points. In further embodiments, thedifference in boiling point between the first and the second solvent maybe from about nil to about 150° C., such as from nil to about 50° C. Forexample, the boiling point of the first solvent may exceed the boilingpoint of the second solvent by about 1° C. to about 100° C., such as byabout 5° C. to about 100° C., or by about 10° C. to about 50° C. Themixed liquid may comprise at least a first and a second solvent withdifferent vapor pressures, such as combinations of high vapor pressuresolvents and/or low vapor pressure solvents. The term “high vaporpressure solvent” refers to, for example, a solvent having a vaporpressure of at least about 1 kPa, such as about 2 kPa, or about 5 kPa.The term “low vapor pressure solvent” refers to, for example, a solventhaving a vapor pressure of less than about 1 kPa, such as about 0.9 kPa,or about 0.5 kPa. In embodiments, the first solvent may be a low vaporpressure solvent such as, for example, terpineol, diethylene glycol,ethylene glycol, hexylene glycol, N-methyl-2-pyrrolidone, andtri(ethylene glycol)dimethyl ether. A high vapor pressure solvent allowsrapid removal of the solvent by drying and/or evaporation attemperatures below the boiling point. High vapor pressure solvents mayinclude, for example, acetone, tetrahydrofuran, toluene, xylene,ethanol, methanol, 2-butanone and water.

In embodiments where mixed liquids comprising a first solvent, secondsolvent, third solvent, and so forth are used in the reaction mixture,promoting the change of the wet film and forming the dry SOF maycomprise, for example, heating the wet film to a temperature above theboiling point of the reaction mixture to form the dry SOF film; orheating the wet film to a temperature above the boiling point of thesecond solvent (below the temperature of the boiling point of the firstsolvent) in order to remove the second solvent while substantiallyleaving the first solvent and then after substantially removing thesecond solvent, removing the first solvent by heating the resultingcomposition at a temperature either above or below the boiling point ofthe first solvent to form the dry SOF film; or heating the wet filmbelow the boiling point of the second solvent in order to remove thesecond solvent (which is a high vapor pressure solvent) whilesubstantially leaving the first solvent and, after removing the secondsolvent, removing the first solvent by heating the resulting compositionat a temperature either above or below the boiling point of the firstsolvent to form the dry SOF film.

The term “substantially removing” refers to, for example, the removal ofat least 90% of the respective solvent, such as about 95% of therespective solvent. The term “substantially leaving” refers to, forexample, the removal of no more than 2% of the respective solvent, suchas removal of no more than 1% of the respective solvent.

These mixed liquids may be used to slow or speed up the rate ofconversion of the wet layer to the SOF in order to manipulate thecharacteristics of the SOFs. For example, in condensation andaddition/elimination linking chemistries, liquids such as water, 1°, 2°,or 3° alcohols (such as methanol, ethanol, propanol, isopropanol,butanol, 1-methoxy-2-propanol, tert-butanol) may be used.

Optionally a catalyst may be present in the reaction mixture to assistthe promotion of the wet layer to the dry SOF. Selection and use of theoptional catalyst depends on the functional groups on the molecularbuilding blocks. Catalysts may be homogeneous (dissolved) orheterogeneous (undissolved or partially dissolved) and include Brönstedacids (HCl (aq), acetic acid, p-toluenesulfonic acid, amine-protectedp-toluenesulfonic acid such as pyrridium p-toluenesulfonate,trifluoroacetic acid); Lewis acids (boron trifluoroetherate, aluminumtrichloride); Brönsted bases (metal hydroxides such as sodium hydroxide,lithium hydroxide, potassium hydroxide; 1°, 2°, or 3° amines such asbutylamine, diisopropylamine, triethylamine, diisoproylethylamine);Lewis bases (N,N-dimethyl-4-aminopyridine); metals (Cu bronze); metalsalts (FeCl₃, AuCl₃); and metal complexes (ligated palladium complexes,ligated ruthenium catalysts). Typical catalyst loading ranges from about0.01% to about 25%, such as from about 0.1% to about 5% of the molecularbuilding block loading in the reaction mixture. The catalyst may or maynot be present in the final SOF composition.

Optionally additives or secondary components, such as dopants, may bepresent in the reaction mixture and wet layer. Such additives orsecondary components may also be integrated into a dry SOF, Additives orsecondary components can be homogeneous or heterogeneous in the reactionmixture and wet layer or in a dry SOF. The terms “additive” or“secondary component,” refer, for example, to atoms or molecules thatare not covalently bound in the SOF, but are randomly distributed in thecomposition. In embodiments, secondary components such as conventionaladditives may be used to take advantage of the known propertiesassociated with such conventional additives. Such additives may be usedto alter the physical properties of the SOF such as electricalproperties (conductivity, semiconductivity, electron transport, holetransport), surface energy (hydrophobicity, hydrophilicity), tensilestrength, and thermal conductivity; such additives may include impactmodifiers, reinforcing fibers, lubricants, antistatic agents, couplingagents, wetting agents, antifogging agents, flame retardants,ultraviolet stabilizers, antioxidants, biocides, dyes, pigments,odorants, deodorants, nucleating agents and the like.

In embodiments, the SOF may contain antioxidants as a secondarycomponent to protect the SOF from oxidation. Examples of suitableantioxidants include (1) N,N′-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy hydrocinnamamide) (IRGANOX 1098,available from Ciba-Geigy Corporation), (2)2,2-bis(4-(2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy))ethoxyphenyl)propane(TOPANOL-205, available from ICI America Corporation), (3)tris(4-tert-butyl-3-hydroxy-2,6-dimethyl benzyl)isocyanurate (CYANOX1790, 41,322-4, LTDP, Aldrich D12, 840-6), (4) 2,2′-ethylidenebis(4,6-di-tert-butylphenyl)fluoro phosphonite (ETHANOX-398, availablefrom Ethyl Corporation), (5)tetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenyl diphosphonite (ALDRICH46, 852-5; hardness value 90), (6) pentaerythritol tetrastearate (TCIAmerica #PO739), (7) tributylammonium hypophosphite (Aldrich 42,009-3),(8) 2,6-di-tert-butyl-4-methoxyphenol (Aldrich 25,106-2), (9)2,4-di-tert-butyl-6-(4-methoxybenzyl)phenol (Aldrich 23,008-1), (10)4-bromo-2,6-dimethylphenol (Aldrich 34, 951-8), (11)4-bromo-3,5-didimethylphenol (Aldrich B6,420-2), (12)4-bromo-2-nitrophenol (Aldrich 30,987-7), (13) 4-(diethylaminomethyl)-2,5-dimethylphenol (Aldrich 14,668-4), (14)3-dimethylaminophenol (Aldrich D14,400-2), (15)2-amino-4-tert-amylphenol (Aldrich 41,258-9), (16)2,6-bis(hydroxymethyl)-p-cresol (Aldrich 22,752-8), (17)2,2′-methylenediphenol (Aldrich B4,680-8), (18)5-(diethylamino)-2-nitrosophenol (Aldrich 26,951-4), (19)2,6-dichloro-4-fluorophenol (Aldrich 28,435-1), (20) 2,6-dibromo fluorophenol (Aldrich 26,003-7), (21) a trifluoro-o-cresol (Aldrich 21,979-7),(22) 2-bromo-4-fluorophenol (Aldrich 30,246-5), (23) 4-fluorophenol(Aldrich F1,320-7), (24) 4-chlorophenyl-2-chloro-1,1,2-tri-fluoroethylsulfone (Aldrich 13,823-1), (25) 3,4-difluoro phenylacetic acid (Aldrich29,043-2), (26) 3-fluorophenylacetic acid (Aldrich 24,804-5), (27)3,5-difluoro phenylacetic acid (Aldrich 29,044-0), (28)2-fluorophenylacetic acid (Aldrich 20,894-9), (29)2,5-bis(trifluoromethyl)benzoic acid (Aldrich 32,527-9), (30)ethyl-2-(4-(4-(trifluoromethyl)phenoxy)phenoxy)propionate (Aldrich25,074-0), (31) tetrakis(2,4-di-tert-butyl phenyl)-4,4′-biphenyldiphosphonite (Aldrich 46,852-5), (32) 4-tert-amyl phenol (Aldrich15,384-2), (33) 3-(2H-benzotriazol-2-yl)-4-hydroxy phenethylalcohol(Aldrich 43,071-4), NAUGARD 76, NAUGARD 445, NAUGARD 512, and NAUGARD524 (manufactured by Uniroyal Chemical Company), and the like, as wellas mixtures thereof. The antioxidant, when present, may be present inthe SOF composite in any desired or effective amount, such as from about0.25 percent to about 10 percent by weight of the SOF or from about 1percent to about 5 percent by weight of the SOF.

In embodiments, the SOF may farther comprise any suitable polymericmaterial known in the art as a secondary component, such aspolycarbonates, acrylate polymers, vinyl polymers, cellulose polymers,polyesters, polysiloxanes, polyamides, polyurethanes, polystyrenes,polystyrene, polyolefins, fluorinated hydrocarbons (fluorocarbons), andengineered resins as well as block, random or alternating copolymersthereof. The SOF composite may comprise homopolymers, higher orderpolymers, or mixtures thereof, and may comprise one species of polymericmaterial or mixtures of multiple species of polymeric material, such asmixtures of two, three, four, five or more multiple species of polymericmaterial. In embodiments, suitable examples of the about polymersinclude, for example, crystalline and amorphous polymers, or a mixturesthereof. In embodiments, the polymer is a fluoroelastomer.

Suitable fluoroelastomers are those described in detail in U.S. Pat.Nos. 5,166,031, 5,281,506, 5,366,772, 5,370,931, 4,257,699, 5,017,432and 5,061,965, the disclosures each of which are incorporated byreference herein in their entirety. The amount of fluoroelastomercompound present in the SOF, in weight percent total solids, is fromabout 1 to about 50 percent, or from about 2 to about 10 percent byweight of the SOF. Total solids, as used herein, includes the amount ofsecondary components and SOF.

In embodiments, examples of styrene-based monomer and acrylate-basedmonomers include, for example, poly(styrene-alkyl acrylate),poly(styrene-1,3-diene), poly(styrene-alkyl methacrylate),poly(styrene-alkyl acrylate-acrylic acid),poly(styrene-1,3-diene-acrylic acid), poly(styrene-alkylmethacrylate-acrylic acid), poly(alkyl methacrylate-alkyl acrylate),poly(alkyl methacrylate-aryl acrylate), poly(aryl methacrylate-alkylacrylate), poly(alkyl methacrylate-acrylic acid), poly(styrene-alkylacrylate-acrylonitrile-acrylic acid),polystyrene-1,3-diene-acrylonitrile-acrylic acid), poly(alkylacrylate-acrylonitrile-acrylic acid), poly(styrene-butadiene),poly(methylstyrene-butadiene), poly(methyl methacrylate-butadiene),poly(ethyl methacrylate-butadiene), poly(propyl methacrylate-butadiene),poly(butyl methacrylate-butadiene), poly(methyl acrylate-butadiene),poly(ethyl acrylate-butadiene), poly(propyl acrylate-butadiene),poly(butyl acrylate-butadiene), polystyrene-isoprene),poly(methylstyrene-isoprene), poly(methyl methacrylate-isoprene),poly(ethyl methacrylate-isoprene), poly(propyl methacrylate-isoprene),poly(butyl methacrylate-isoprene), poly(methyl acrylate-isoprene),poly(ethyl acrylate-isoprene), poly(propyl acrylate-isoprene), andpoly(butyl acrylate-isoprene); poly(styrene-propyl acrylate),poly(styrene-butyl acrylate), poly(styrene-butadiene-acrylic acid),poly(styrene-butadiene-methacrylic acid),polystyrene-butadiene-acrylonitrile-acrylic acid), poly(styrene-butylacrylate-acrylic acid), poly(styrene-butyl acrylate-methacrylic acid),poly(styrene-butyl acrylate-acrylonitrile), poly(styrene-butylacrylate-acrylonitrile-acrylic acid), and other similar polymers.

Further examples of the various polymers that are suitable for use as asecondary component in SOFs include polyethylene terephthalate,polybutadienes, polysulfones, polyarylethers, polyarylsulfones,polyethersulfones, polycarbonates, polyethylenes, polypropylenes,polydecene, polydodecene, polytetradecene, polyhexadecene, polyoctadene,and polycyclodecene, polyolefin copolymers, mixtures of polyolefins,functional polyolefins, acidic polyolefins, branched polyolefins,polymethylpentenes, polyphenylene sulfides, polyvinyl acetates,polyvinylbutyrals, polysiloxanes, polyacrylates, polyvinyl acetals,polyamides, polyimides, polystyrene and acrylonitrile copolymers,polyvinylchlorides, polyvinyl alcohols, poly-N-vinylpyrrolidinone)s,vinylchloride and vinyl acetate copolymers, acrylate copolymers,poly(amideimide), styrene-butadiene copolymers,vinylidenechloride-vinylchloride copolymers,vinylacetate-vinylidenechloride copolymers, polyvinylcarbazoles,polyethylene-terephthalate, polypropylene-terephthalate,polybutylene-terephthalate, polypentylene-terephthalate,polyhexylene-terephthalate, polyheptadene-terephthalate,polyoctalene-terephthalate, polyethylene-sebacate, polypropylenesebacate, polybutylene-sebacate, polyethylene-adipate,polypropylene-adipate, polybutylene-adipate, polypentylene-adipate,polyhexylene-adipate, polyheptadene-adipate, polyoctalene-adipate,polyethylene-glutarate, polypropylene-glutarate, polybutylene-glutarate,polypentylene-glutarate, polyhexylene-glutarate,polyheptadene-glutarate, polyoctalene-glutarate polyethylene-pimelate,polypropylene-pimelate, polybutylene-pimelate, polypentylene-pimelate,polyhexylene-pimelate, polyheptadene-pimelate, poly(propoxylatedbisphenol-fumarate), poly(propoxylated bisphenol-succinate),poly(propoxylated bisphenol-adipate), poly(propoxylatedbisphenol-glutarate), SPAR™ (Dixie Chemicals), BECKOSOL™ (ReichholdChemical Inc), ARAKOTE™ (Ciba-Geigy Corporation), HETRON™ (AshlandChemical), PARAPLEX™ (Rohm & Hass), POLYLITE™ (Reichhold Chemical Inc),PLASTHALL™ (Rohm & Hass), CYGAL™ (American Cyanamide), ARMCO™ (ArmcoComposites), ARPOL™ (Ashland Chemical), CELANEX™ (Celanese Eng), RYNITE™(DuPont), STYPOL™ (Freeman Chemical Corporation) mixtures thereof andthe like.

In embodiments, the secondary components, including polymers may bedistributed homogeneously, or heterogeneously, such as in a linear ornonlinear gradient in the SOF. In embodiments, the polymers may beincorporated into the SOF in the form of a fiber, or a particle whosesize may range from about 50 nm to about 2 mm. The polymers, whenpresent, may be present in the SOF composite in any desired or effectiveamount, such as from about 1 percent to about 50 percent by weight ofthe SOF or from about 1 percent to about 15 percent by weight of theSOF.

In embodiments, the SOF may further comprise carbon nanotubes ornanofiber aggregates, which are microscopic particulate structures ofnanotubes, as described in U.S. Pat. Nos. 5,165,909; 5,456,897;5,707,916; 5,877,110; 5,110,693; 5,500,200 and 5,569,635, all of whichare hereby entirely incorporated by reference.

In embodiments, the SOF may further comprise metal particles as asecondary component; such metal particles include noble and non-noblemetals and their alloys. Examples of suitable noble metals include,aluminum, titanium, gold, silver, platinum, palladium and their alloys.Examples of suitable non-noble metals include, copper, nickel, cobalt,lead, iron, bismuth, zinc, ruthenium, rhodium, rubidium, indium, andtheir alloys. The size of the metal particles may range from about 1 nmto 1 mm and their surfaces may be modified by stabilizing molecules ordispersant molecules or the like. The metal particles, when present, maybe present in the SOF composite in any desired or effective amount, suchas from about 0.25 percent to about 70 percent by weight of the SOF orfrom about 1 percent to about 15 percent by weight of the SOF.

In embodiments, the SOF may further comprise oxides and sulfides assecondary components. Examples of suitable metal oxides include,titanium dioxide (titanic, rutile and related polymorphs), aluminumoxide including alumina, hydradated alumina, and the like, silicon oxideincluding silica, quartz, cristobalite, and the like, aluminosilicatesincluding zeolites, talcs, and clays, nickel oxide, iron oxide, cobaltoxide. Other examples of oxides include glasses, such as silica glass,borosilicate glass, aluminosilicate glass and the like. Examples ofsuitable sulfides include nickel sulfide, lead sulfide, cadmium sulfide,tin sulfide, and cobalt sulfide. The diameter of the oxide and sulfidematerials may range from about 50 nm to 1 mm and their surfaces may bemodified by stabilizing molecules or dispersant molecules or the like.The oxides, when present, may be present in the SOF composite in anydesired or effective amount, such as from about 0.25 percent to about 20percent by weight of the SOF or from about 1 percent to about 15 percentby weight of the SOF.

In embodiments, the SOF may further comprise metalloid or metal-likeelements from the periodic table. Examples of suitable metalloidelements include, silicon, selenium, tellurium, tin, lead, germanium,gallium, arsenic, antimony and their alloys or intermetallics. The sizeof the metal particles may range from about 10 nm to 1 mm and theirsurfaces may be modified by stabilizing molecules or dispersantmolecules or the like. The metalloid particles, when present, may bepresent in the SOF composite in any desired or effective amount, such asfrom about 0.25 percent to about 10 percent by weight of the SOF or fromabout 1 percent to about 5 percent by weight of the SOF.

In embodiments, the SOF may further comprise hole transport molecules orelectron acceptors as a secondary component, such charge transportmolecules include for example a positive hole transporting materialselected from compounds having in the main chain or the side chain apolycyclic aromatic ring such as anthracene, pyrene, phenanthrene,coronene, and the like, or a nitrogen-containing hetero ring such asindole, carbazole, oxazole, isoxazole, thiazole, imidazole, pyrazole,oxadiazole, pyrazoline, thiadiazole, triazole, and hydrazone compounds.Typical hole transport materials include electron donor materials, suchas carbazole; N-ethyl carbazole; N-isopropyl carbazole; N-phenylcarbazole; tetraphenylpyrene; 1-methylpyrene; perylene; chrysene;anthracene; tetraphene; 2-phenyl naphthalene; azopyrene; 1-ethyl pyrene;acetyl pyrene; 2,3-benzochrysene; 2,4-benzopyrene; 1,4-bromopyrene;poly(N-vinylcarbazole); poly(vinylpyrene); poly(vinyltetraphene);poly(vinyltetracene) and poly(vinylperylene). Suitable electrontransport materials include electron acceptors such as2,4,7-trinitro-9-fluorenone; 2,4,5,7-tetranitro-fluorenone;dinitroanthracene; dinitroacridene; tetracyanopyrene;dinitroanthraquinone; and butylcarbonylfluorenemalononitrile, see U.S.Pat. No. 4,921,769 the disclosure of which is incorporated herein byreference in its entirety. Other hole transporting materials includearylamines described in U.S. Pat. No. 4,265,990 the disclosure of whichis incorporated herein by reference in its entirety, such asN,N′-diphenyl-N,N′-bis(alkylphenyl)-(1,1′-biphenyl)-4,4′-diamine whereinalkyl is selected from the group consisting of methyl, ethyl, propyl,butyl, hexyl, and the like. Hole transport molecules of the typedescribed in, for example, U.S. Pat. Nos. 4,306,008; 4,304,829;4,233,384; 4,115,116; 4,299,897; 4,081,274, and 5,139,910, the entiredisclosures of each are incorporated herein by reference. Other knowncharge transport layer molecules may be selected, reference for exampleU.S. Pat. Nos. 4,921,773 and 4,464,450 the disclosures' of which areincorporated herein by reference in their entireties. The hole transportmolecules or electron acceptors, when present, may be present in the SOFcomposite in any desired or effective amount, such as from about 0.25percent to about 50 percent by weight of the SOF or from about 1 percentto about 20 percent by weight of the SOF.

In embodiments, the SOF may further comprise biocides as a secondarycomponent. Biocides may be present in amounts of from about 0.1 to about1.0 percent by weight of the SOF. Suitable biocides include, forexample, sorbic acid, 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantanechloride, commercially available as DOWICIL 200 (Dow Chemical Company),vinylene-bis thiocyanate, commercially available as CYTOX 3711 (AmericanCyanamid Company), disodium ethylenebis-dithiocarbamate, commerciallyavailable as DITHONE D14 (Rohm & Haas Company),bis(trichloromethyl)sulfone, commercially available as BIOCIDE N-1386(Stauffer Chemical Company), zinc pyridinethione, commercially availableas zinc omadine (Olin Corporation), 2-bromo-t-nitropropane-1,3-diol,commercially available as ONYXIDE 500 (Onyx Chemical Company), BOSQUATMB50 (Louza, Inc.), and the like.

In embodiments, the SOF may further comprise small organic molecules asa secondary component; such small organic molecules include thosediscussed above with respect to the first and second solvents. The smallorganic molecules, when present, may be present in the SOF in anydesired or effective amount, such as from about 0.25 percent to about 50percent by weight of the SOF or from about 1 percent to about 10 percentby weight of the SOF.

When present, the secondary components or additives may each, or incombination, be present in the composition in any desired or effectiveamount, such as from about 1 percent to about 50 percent by weight ofthe composition or from about 1 percent to about 20 percent by weight ofthe composition.

SOFs may be modified with secondary components (dopants and additives,such as, hole transport molecules (mTBD), polymers (polystyrene),nanoparticles (C60 Buckminster fullerene), small organic molecules(biphenyl), metal particles (copper micropowder), and electron acceptors(quinone)) to give composite structured organic films. Secondarycomponents may be introduced to the liquid formulation that is used togenerate a wet film in which a change is promoted to form the SOF.Secondary components (dopants, additives, etc.) may either be dissolvedor undissolved (suspended) in the reaction mixture. Secondary componentsare not bonded into the network of the film. For example, a secondarycomponent may be added to a reaction mixture that contains a pluralityof building blocks having four methoxy groups (—OMe) on a segment, suchas N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine, which uponpromotion of a change in the wet film, exclusively react with the twoalcohol (—OH) groups on a building block, such as 1,4-benzenedimethanol,which contains a p-xylyl segment. The chemistry that is occurring tolink building blocks is an acid catalyzed transetherfication reaction.Because —OH groups will only react with —OMe groups (and vice versa) andnot with the secondary component, these molecular building blocks canonly follow one pathway. Therefore, the SOF is programmed to ordermolecules in a way that leaves the secondary component incorporatedwithin and/or around the SOF structure. This ability to patternmolecules and incorporate secondary components affords superiorperformance and unprecedented control over properties compared toconventional polymers and available alternatives.

Optionally additives or secondary components, such as dopants, may bepresent in the reaction mixture and wet layer. Such additives orsecondary components may also be integrated into a dry SOF. Additives orsecondary components can be homogeneous or heterogeneous in the reactionmixture and wet layer or in a dry SOF. In contrast to capping units, theterms “additive” or “secondary component,” refer, for example, to atomsor molecules that are not covalently bound in the SOF, but are randomlydistributed in the composition. Suitable secondary components andadditives are described in U.S. patent application Ser. No. 12/716,324,entitled “Composite Structured Organic Films,” the disclosure of whichis totally incorporated herein by reference in its entirety.

In embodiments, the secondary components may have similar or disparateproperties to accentuate or hybridize (synergistic effects orameliorative effects as well as the ability to attenuate inherent orinclined properties of the capped SOF) the intended property of thecapped SOF to enable it to meet performance targets. For example, dopingthe capped SOFs with antioxidant compounds will extend the life of thecapped SOF by preventing chemical degradation pathways. Additionally,additives maybe added to improve the morphological properties of thecapped SOF by tuning the reaction occurring during the promotion of thechange of the reaction mixture to form the capped SOF.

Process Action B: Depositing the Reaction Mixture as a Wet Film

The reaction mixture may be applied as a wet film to a variety ofsubstrates, such as print head front faces, using a number of liquiddeposition techniques. Alternatively, the coating comprising the SOF maybe prepared and then attached to the print head front face. Thethickness of the SOF is dependant on the thickness of the wet film andthe molecular building block loading in the reaction mixture. Thethickness of the wet film is dependent on the viscosity of the reactionmixture and the method used to deposit the reaction mixture as a wetfilm.

Substrates include, for example, polymers, papers, metals and metalalloys, doped and undoped forms of elements from Groups III-VI of theperiodic table, metal oxides, metal chalcogenides, and previouslyprepared SOFs or capped SOFs. Examples of polymer film substratesinclude polyesters, polyolefins, polycarbonates, polystyrenes,polyvinylchloride, block and random copolymers thereof, and the like.Examples of metallic surfaces include metallized polymers, metal foils,metal plates; mixed material substrates such as metals patterned ordeposited on polymer, semiconductor, metal oxide, or glass substrates.Examples of substrates comprised of doped and undoped elements fromGroups III-VI of the periodic table include, aluminum, silicon, siliconn-doped with phosphorous, silicon p-doped with boron, tin, galliumarsenide, lead, gallium indium phosphide, and indium. Examples of metaloxides include silicon dioxide, titanium dioxide, indium tin oxide, tindioxide, selenium dioxide, and alumina. Examples of metal chalcogenidesinclude cadmium sulfide, cadmium telluride, and zinc selenide.Additionally, it is appreciated that chemically treated or mechanicallymodified forms of the above substrates remain within the scope ofsurfaces that may be coated with the reaction mixture.

In embodiments, the substrate may be composed of, for example, silicon,glass plate, plastic film or sheet. For structurally flexible devices, aplastic substrate such as polyester, polycarbonate, polyimide sheets andthe like may be used. The thickness of the substrate may be from around10 micrometers to over 10 millimeters with an exemplary thickness beingfrom about 50 to about 100 micrometers, especially for a flexibleplastic substrate, and from about 1 to about 10 millimeters for a rigidsubstrate such as glass or silicon.

The reaction mixture may be applied to the substrate using a number ofliquid deposition techniques including, for example, spin coating, bladecoating, web coating, dip coating, cup coating, rod coating, screenprinting, ink jet printing, spray coating, stamping and the like. Themethod used to deposit the wet layer depends on the nature, size, andshape of the substrate and the desired wet layer thickness. Thethickness of the wet layer can range from about 10 nm to about 5 mm,such as from about 100 nm to about 1 mm, or from about 1 μm to about 500μm.

In embodiments, the capping unit and/or secondary component may beintroduced following completion of the above described process action B.The incorporation of the capping unit and/or secondary component in thisway may be accomplished by any means that serves to distribute thecapping unit and/or secondary component homogeneously, heterogeneously,or as a specific pattern over the wet film. Following introduction ofthe capping unit and/or secondary component subsequent process actionsmay be carried out resuming with process action C.

For example, following completion of process action B (i.e., after thereaction mixture may be applied to the substrate), capping unit(s)and/or secondary components (dopants, additives, etc.) may be added tothe wet layer by any suitable method, such as by distributing (e.g.,dusting, spraying, pouring, sprinkling, etc, depending on whether thecapping unit and/or secondary component is a particle, powder or liquid)the capping unit(s) and/or secondary component on the top the wet layer.The capping units and/or secondary components may be applied to theformed wet layer in a homogeneous or heterogeneous manner, includingvarious patterns, wherein the concentration or density of the cappingunit(s) and/or secondary component is reduced in specific areas, such asto form a pattern of alternating bands of high and low concentrations ofthe capping unit(s) and/or secondary component of a given width on thewet layer. In embodiments, the application of the capping unit(s) and/orsecondary component to the top of the wet layer may result in a portionof the capping unit(s) and/or secondary component diffusing or sinkinginto the wet layer and thereby forming a heterogeneous distribution ofcapping unit(s) and/or secondary component within the thickness of theSOF, such that a linear or nonlinear concentration gradient may beobtained in the resulting SOF obtained after promotion of the change ofthe wet layer to a dry SOF. In embodiments, a capping unit(s) and/orsecondary component may be added to the top surface of a deposited wetlayer, which upon promotion of a change in the wet film, results in anSOF having an heterogeneous distribution of the capping unit(s) and/orsecondary component in the dry SOF. Depending on the density of the wetfilm and the density of the capping unit(s) and/or secondary component,a majority of the capping unit(s) and/or secondary component may end upin the upper half (which is opposite the substrate) of the dry SOF or amajority of the capping unit(s) and/or secondary component may end up inthe lower half (which is adjacent to the substrate) of the dry SOF.

Process Action C: Promoting the Change of Wet Film to the Dry SOF

The term “promoting” refers, for example, to any suitable technique tofacilitate a reaction of the molecular building blocks and/or pre-SOFs,such as a chemical reaction of the functional groups of the buildingblocks and/or pre-SOFs. In the case where a liquid needs to be removedto form the dry film, “promoting” also refers to removal of the liquid.Reaction of the molecular building blocks and/or pre-SOFs and removal ofthe liquid can occur sequentially or concurrently. In certainembodiments, the liquid is also one of the molecular building blocks andis incorporated into the SOF. The term “dry SOF” refers, for example, tosubstantially dry SOFs, for example, to a liquid content less than about5% by weight of the SOF, or to a liquid content less than 2% by weightof the SOF.

In embodiments, the dry SOF or a given region of the dry SOF (such asthe surface to a depth equal to of about 10% of the thickness of the SOFor a depth equal to of about 5% of the thickness of the SOF, the upperquarter of the SOF, or the regions discussed above) has a molar ratio ofcapping units to segments of from about 1:100 to about 1:1, such as fromabout 1:50 to about 1:2, or from about 1:20 to 1:4.

Promoting the wet layer to form a dry SOF may be accomplished by anysuitable technique. Promoting the wet layer to form a dry SOF typicallyinvolves thermal treatment including, for example, oven drying, infraredradiation (IR), and the like with temperatures ranging from 40 to 350°C. and from 60 to 200° C. and from 85 to 160° C. The total heating timecan range from about four seconds to about 24 hours, such as from oneminute to 120 minutes, or from three minutes to 60 minutes.

In embodiments where a secondary component is present, the molecularsize of the secondary component may be selected such that during thepromotion of the wet layer to form a dry SOF the secondary component istrapped within the framework of the SOF such that the trapped secondarycomponent will not leach from the SOF during exposure to a liquid toneror solvent.

IR promotion of the wet layer to the COF film may be achieved using anIR heater module mounted over a belt transport system. Various types ofER emitters may be used, such as carbon IR emitters or short wave IRemitters (available from Heraerus). Additional exemplary informationregarding carbon IR emitters or short wave IR emitters is summarized inthe following Table (Table 1).

TABLE 1 Information regarding carbon IR emitters or short wave IRemitters Number of Module Power IR lamp Peak Wavelength lamps (kW)Carbon 2.0 micron 2 - twin tube 4.6 Short wave 1.2-1.4 micron 3 - twintube 4.5

Process Action D: Optionally Removing the SOF from the Coating Substrateto Obtain a Free-Standing SOF

In embodiments, a free-standing SOF is desired. Free-standing SOFs maybe obtained when an appropriate low adhesion substrate is used tosupport the deposition of the wet layer. Appropriate substrates thathave low adhesion to the SOF may include, for example, metal foils,metalized polymer substrates, release papers and SOFs, such as SOFsprepared with a surface that has been altered to have a low adhesion ora decreased propensity for adhesion or attachment. Removal of the SOFfrom the supporting substrate may be achieved in a number of ways bysomeone skilled in the art. For example, removal of the SOF from thesubstrate may occur by starting from a corner or edge of the film andoptionally assisted by passing the substrate and SOF over a curvedsurface.

Process Action E: Optionally Processing the Free-Standing SOF into aRoll

Optionally, a free-standing SOF or a SOF supported by a flexiblesubstrate may be processed into a roll. The SOF may be processed into aroll for storage, handling, and a variety of other purposes. Thestarting curvature of the roll is selected such that the SOF is notdistorted or cracked during the rolling process.

Process Action F: Optionally Cutting and Seaming the SOF into a Shape,Such as a Belt

The method for cutting and seaming the SOF is similar to that describedin U.S. Pat. No. 5,455,136 issued on Oct. 3, 1995 (for polymer films),the disclosure of which is herein totally incorporated by reference. AnSOF belt may be fabricated from a single SOF, a multi layer SOF or anSOF sheet cut from a web. Such sheets may be rectangular in shape or anyparticular shape as desired. All sides of the SOF(s) may be of the samelength, or one pair of parallel sides may be longer than the other pairof parallel sides. The SOF(s) may be fabricated into shapes, such as abelt by overlap joining the opposite marginal end regions of the SOFsheet. A seam is typically produced in the overlapping marginal endregions at the point of actively vented oven preheated to 155° C. andleft to heat for 40 minutes. These actions provided an SOF having athickness of 6-8 microns that could be delaminated from substrate as asingle free-standing film. The color of the SOF was amber.

EXAMPLE 4

-   -   (Action A) Preparation of the liquid containing reaction        mixture. The following were combined: the building block        hexadecafluoro-1,10-decanediol        [segment=hexadecafluoro-1,10-decyl; Fg=hydroxyl (—OH); (0.57 g,        1.23 mmol)], a second building block        N4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine        [segment=N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine;        Fg=methoxy ether (—OCH₃); (0.41 g, 0.62 mmol)], an acid catalyst        delivered as 0.05 g of a 20 wt % solution of Nacure XP-357 to        yield the liquid containing reaction mixture, a leveling        additive delivered as 0.04 g of a 25 wt % solution of Silclean        3700, and 2.96 g of 1-methoxy-2-propanol. The mixture was shaken        and heated at 85° C. for 2.5 hours, and was then filtered        through a 0.45 micron PTFE membrane.

(Action B) Deposition of reaction mixture as a wet film. The reactionmixture was applied to the reflective side of a metalized (Tilt) MYLAR™substrate using a constant velocity draw down coater outfitted with abird bar having a 10 mil gap.

(Action C) Promotion of the change of the wet film to a dry SOF. Themetalized MYLAR™ substrate supporting the wet layer was rapidlytransferred to an actively vented oven preheated to 155° C. and left toheat for 40 minutes. These actions provided an SOF having a thickness of6-8 micrometers that could be delaminated from substrate as a singlefree-standing film. The color of the SOF was amber.

The SOFs made high quality films when coated on stainless steel andpolyimide substrates. The SOFs could be handled, rubbed, and flexedwithout any damage/delaminating from the substrate.

Solid Ink joining. Joining may be affected by any suitable means.Typical joining techniques include, for example, welding (includingultrasonic), gluing, taping, pressure heat fusing and the like. Methods,such as ultrasonic welding, are desirable general methods of joiningflexible sheets because of their speed, cleanliness (no solvents) andproduction of a thin and narrow seam.

Process Action G: Optionally Using a SOF as a Substrate for SubsequentSOF Formation Processes

A SOF may be used as a substrate in the SOF forming process to afford amulti-layered structured organic film. The layers of a multi-layered SOFmay be chemically bound in or in physical contact. Chemically bound,multi-layered SOFs are formed when functional groups present on thesubstrate SOF surface can react with the molecular building blockspresent in the deposited wet layer used to form the second structuredorganic film layer. Multi-layered SOFs in physical contact may notchemically bound to one another.

A SOF substrate may optionally be chemically treated prior to thedeposition of the wet layer to enable or promote chemical attachment ofa second SOF layer to form a multi-layered structured organic film.

Alternatively, a SOF substrate may optionally be chemically treatedprior to the deposition of the wet layer to disable chemical attachmentof a second SOF layer (surface pacification) to form a physical contactmulti-layered SOF.

Other methods, such as lamination of two or more SOFs, may also be usedto prepare physically contacted multi-layered SOFs.

Patterned SOF Composition

An embodiment of the disclosure is to attain a SOF wherein themicroscopic arrangement of segments is patterned. The term “patterning”refers, for example, to the sequence in which segments are linkedtogether. A patterned SOF would therefore embody a composition wherein,for example, segment A is only connected to segment B, and conversely,segment B is only connected to segment A. Further, a system wherein onlyone segment exists, say segment A, is employed is will be patternedbecause A is intended to only react with A. In principle a patterned SOFmay be achieved using any number of segment types. The patterning ofsegments may be controlled by using molecular building blocks whosefunctional group reactivity is intended to compliment a partnermolecular building block and wherein the likelihood of a molecularbuilding block to react with itself is minimized. The aforementionedstrategy to segment patterning is non-limiting. Instances where aspecific strategy to control patterning has not been deliberatelyimplemented are also embodied herein.

A patterned film may be detected using spectroscopic techniques that arecapable of assessing the successful formation of linking groups in aSOF. Such spectroscopies include, for example, Fourier-transfer infraredspectroscopy, Raman spectroscopy, and solid-state nuclear magneticresonance spectroscopy. Upon acquiring a data by a spectroscopictechnique from a sample, the absence of signals from functional groupson building blocks and the emergence of signals from linking groupsindicate the reaction between building blocks and the concomitantpatterning and formation of an SOF.

Different degrees of patterning are also embodied. Full patterning of aSOF will be detected by the complete absence of spectroscopic signalsfrom building block functional groups. Also embodied are SOFs havinglowered degrees of patterning wherein domains of patterning exist withinthe SOF. SOFs with domains of patterning, when measuredspectroscopically, will produce signals from building block functionalgroups which remain unmodified at the periphery of a patterned domain.

It is appreciated that a very low degree of patterning is associatedwith inefficient reaction between building blocks and the inability toform a film. Therefore, successful implementation of the process of thepresent disclosure requires appreciable patterning between buildingblocks within the SOF. The degree of necessary patterning to form a SOFis variable and can depend on the chosen building blocks and desiredlinking groups. The minimum degree of patterning required is thatrequired to form a film using the process described herein, and may bequantified as formation of about 20% or more of the intended linkinggroups, such as about 40% or more of the intended linking groups orabout 50% or more of the intended linking groups; the nominal degree ofpatterning embodied by the present disclosure is formation of about 60%of the intended linking group, such as formation of about 100% of theintended linking groups. Formation of linking groups may be detectedspectroscopically as described earlier in the embodiments.

Production of a Coating Comprising an SOF

EXAMPLE 1

(Action A) Preparation of the liquid containing reaction mixture. Thefollowing were combined: the building blockN,N,N′,N′-tetrakis-[(4-hydroxymethyl)phenyl]-biphenyl-4,4′-diamine (2.64g); the building blockN,N′-bis-(3-hydroxyphenyl)-N,N′-diphenyl-biphenyl-4,4′-diamine (3.73 g);the additive Cymel 303 (67 mg), the additive Silclean 3700 (264 mg), thecatalyst Nacure 5225 (132 mg) and Dowanol (18.48 g). The mixture wasshaken and heated to 55° C. for 60 minutes. Upon cooling to roomtemperature, the solution was filtered through a five micron PTFEmembrane.

(Action B) Deposition of reaction mixture as a wet film. The reactionmixture was applied to a substrate (either polyimide or stainless steelsheets) using a constant velocity draw-down coater outfitted with a birdbar having a 2 mil gap.

(Action C) Promotion of the change of the wet film to a dry SOF. Thesubstrate (polyimide and stainless steel sheets) supporting the wetlayer was rapidly transferred to an actively vented oven preheated to155° C. and left to heat for 40 minutes to afford the desired SOF.

EXAMPLE 2

(Action A) Preparation of the liquid containing reaction mixture. Thefollowing were combined: the building block octafluoro-1,6-hexanediol[segment=octafluoro-1,6-hexyl; Fg=hydroxyl (—OH); (0.43 g, 1.65 mmol)],a second building blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment=N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine; Fg=methoxyether (—OCH₃); (0.55 g, 0.82 mmol)], an acid catalyst delivered as 0.05g of a 20 wt % solution of Nacure XP-357 to yield the liquid containingreaction mixture, a leveling additive delivered as 0.04 g of a 25 wt %solution of Silclean 3700, and 2.96 g of 1-methoxy-2-propanol. Themixture was shaken and heated at 85° C. for 2.5 hours, and was thenfiltered through a 0.45 micron PTFE membrane.

(Action B) Deposition of reaction mixture as a wet film. The reactionmixture was applied to the reflective side of a metalized (TiZr) MYLAR™substrate using a constant velocity draw down coater outfitted with abird bar having a 10 mil gap.

(Action C) Promotion of the change of the wet film to a dry SOF. Themetalized MYLAR™ substrate supporting the wet layer was rapidlytransferred to an actively vented oven preheated to 155° C. and left toheat for 40 minutes. These actions provided an SOF having a thickness of6-8 microns that could be delaminated from substrate as a singlefree-standing film. The color of the SOF was amber.

EXAMPLE 3

(Action A) Preparation of the liquid containing reaction mixture. Thefollowing were combined: the building block dodecafluoro-1,8-octanediol[segment=dodecafluoro-1,8-octyl; Fg=hydroxyl (—OH); (0.51 g, 1.41mmol)], a second building blockN4,N4,N4′,N4′-tetrakis(4-(methoxymethyl)phenyl)biphenyl-4,4′-diamine[segment=N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine; Fg=methoxyether (—OCH₃); (0.47 g, 0.71 mmol)], an acid catalyst delivered as 0.05g of a 20 wt % solution of Nacure XP-357 to yield the liquid containingreaction mixture, a leveling additive delivered as 0.04 g of a 25 wt %solution of Silclean 3700, and 2.96 g of 1-methoxy-2-propanol. Themixture was shaken and heated at 85° C. for 2.5 hours, and was thenfiltered through a 0.45 micron PTFE membrane.

(Action B) Deposition of reaction mixture as a wet film. The reactionmixture was applied to the reflective side of a metalized (TiZr) MYLAR™substrate using a constant velocity draw down coater outfitted with abird bar having a 10 mil gap.

(Action C) Promotion of the change of the wet film to a dry SOF. Themetalized MYLAR™ substrate supporting the wet layer was rapidlytransferred to an

The tests described below were carried out on two magenta inkscontaining different pigments and one yellow ink. Pigments (˜2-3% offormulation) are often a source of interactions between inks and faceplate surfaces, and magenta has been shown to display increased adhesionissues compared with other pigments, which is why magenta inks wereprimarily tested. Surface adhesion could, however, result from any orall components in a solid ink formulation. Generally, solid inks testedare amide wax-based inks with pigment where the wax ispolyethylene-based or could be polyester-based. There are approximatelyequal proportions (50/50) of wax and waxy-amides in the inks tested.Dispersants are present in 1-1.5 ratio compared to pigment, and comprisefunctional head groups and internal functionalities that can be amines,amino salts, esters or other functionalities with wax-like alkyl chainssuch as polyethylene.

UV Ink

The tests described below were carried out on a UV curable phase changecyan ink and ink base. The cyan ink of the example is acrylate-basedcontaining both difunctional and multifunctional acrylates. The ink alsooptionally contains a curable wax, that could alternatively be polyesteror other waxy chains, and an organic gellator. UV inks also containphotoinitiators such as phosphine oxides, alpha-hydroxyketones,alpha-aminoketones and the like and a radical stabilizer such asnitroxide radical stabilizer. Also present are pigments and dispersants,that could contain a block copolymer, although this coating is alsoapplicable for use with unpigmented systems.

Evaluation: Contact Angle & Surface Energy Measurements

Contact angle measurements were made using three solvents—water,formaldehyde, and diiodomethane.

Samples were cut into 15 mm×50-145 mm by double blade cutter. Samplethickness should be less than 1.5 mm using standard holder and less than5.0 mm using homemade special holder. Sample was mounted onto the sampleholder with double sides tape. Three testing liquids were usedthroughout the contact angle measurements, water, formamide anddiiodomethane.

Around 8 drops were generated depending on the sample availability andthe contact angle was measured. The average contact angle for 0.1 s, 1 sand 10 s data were recorded. The surface free energy, acid and basecomponents of the polar surface energy as well as the dispersivecomponent were calculated using Lewis acid-base method. Lewis acid-basetheory is given by the following equation for the solid-liquidinterfacial energy.

${y_{j}\left( {1 + {\cos\;\theta_{j}}} \right)} = {{2\left( {\gamma_{s}^{LW}\gamma_{j}^{LW}} \right)^{\frac{1}{2}}} + {2\left( {\gamma_{s}^{-}\gamma_{j}^{+}} \right)^{\frac{1}{2}}} + {2\left( {\gamma_{s}^{+}\gamma_{j}^{-}} \right)^{\frac{1}{2}}}}$where (LW), (+), (−) are the dispersive, acid and base components of theSFE index, j refers to liquids 1, 2, 3. θ_(j) is the contact angle ofthe jth liquid on the substrate. γ_(j) is the surface tension of liquidj, and subscript s refers to the solid. The surface free energy was alsodetermined to be 28.39 mN/m for the SOF of Example 1. The contact anglemeasurements are summarized in Table 2 below.

TABLE 2 Contact angle measurements (degrees) Water formaldehydediiodomethane 0.1 s 1 s 10 s 0.1 s 1 s 10 s 0.1 s 1 s 10 s SOF 97.0 97.096.3 84.5 84.4 84.6 64.7 64.5 64.1

Ink Drop Wicking Test

The SOF-coated polyimide and stainless steel substrates were placed onan aluminum plate and heated to 120° C. Inks and ink components testedfor solid ink adhesion included formulations of solid inks containingmagenta pigment, and synergist formulations containing yellow pigment ormagenta pigment. Two drops of each melted solid ink sample ranging fromlow to high drool were placed on the SOF samples (from Example 1). Onedrop from each ink was removed by dabbing with a Q-tip within 2 minutesof being placed on the SOF (time zero). The second drop from each inksample was left at 120° C. for 24 hours. Then the second drop wasremoved by dabbing the drop with a Q-tip. There was no observabledifference between the time zero and 24 hour ink drop removal. Theentire ink drop could be removed by touching a Q-tip to the drop 2-4times (limited by the size/wetting of the Q-tip).

It will be appreciated that several of the above-disclosed and otherfeatures and functions, or alternatives thereof, may be desirablycombined into many other different systems or applications. Variouspresently unforeseen or unanticipated alternatives, modifications,variations or improvements therein may be subsequently made by thoseskilled in the art which are also intended to be encompassed by thefollowing claims. Unless specifically recited in a claim, steps orcomponents of claims should not be implied or imported from thespecification or any other claims as to any particular order, number,position, size, shape, angle, color, or material.

1. A coating for an ink jet printhead front face, the coating comprisinga structured organic film (SOF) comprising a plurality of segments, aplurality of linkers arranged as a covalent organic framework (COF). 2.The coating of claim 1, wherein jetted drops of a UV curable ink orjetted drops of solid ink on the ink jet printhead front face exhibit acontact angle of about a contact angle of from about 140° to about 60°.3. The coating of claim 2, wherein the contact angle is from about 110°to about 75°.
 4. The coating of claim 3, wherein the SOF is afluorinated SOF.
 5. The coating of claim 1, wherein the SOF is acomposite SOF.
 6. The coating of claim 1, wherein the SOF has an addedfunctionality.
 7. The coating of claim 1, wherein the SOF comprises acapping unit.
 8. An ink jet printhead comprising: a front face havingdisposed on a surface thereof a coating, the coating comprising astructured organic film (SOF) comprising a plurality of segments, aplurality of linkers arranged as a covalent organic framework (COF). 9.The ink jet printhead of claim 8, wherein jetted drops of a UV curableink or jetted drops of solid ink on the ink jet printhead front faceexhibit a contact angle of about a contact angle of from about 140° toabout 60°.
 10. The ink jet printhead of claim 9, wherein the contactangle is from about 110° to about 75°.
 11. The ink jet printhead ofclaim 8, wherein the SOF is a fluorinated SOF.
 12. The ink jet printheadof claim 8, wherein the SOF is a composite SOF.
 13. The ink jetprinthead of claim 8, wherein the SOF has an added functionality. 14.The ink jet printhead of claim 8, wherein the SOF comprises a cappingunit.
 15. An apparatus for printing comprising: the ink jet print headof claim
 8. 16. The apparatus for printing of claim 15, wherein jetteddrops of a UV curable ink or jetted drops of solid ink on the ink jetprinthead front face exhibit a contact angle of about a contact angle offrom about 140° to about 60°.
 17. The apparatus for printing of claim15, wherein the contact angle is from about 110° to about 75°.
 18. Theapparatus for printing of claim 15, wherein the SOF is a fluorinatedSOF.
 19. A method for making an ink jet printhead nozzle platecomprising: providing a plate substrate; and forming a coatingcomprising a structured organic film (SOF) comprising a plurality ofsegments, a plurality of linkers arranged as a covalent organicframework (COF) on the plate substrate.
 20. The method of claim 19,wherein forming a coating comprises: (a) preparing a liquid-containingreaction mixture comprising: a solvent, and a plurality of molecularbuilding blocks each comprising a segment and functional groups; (b)depositing the reaction mixture as a wet film; and (c) promoting achange of the wet film and forming a dry SOF.